Applied Surface Science 365 (2016) 209–217

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Applied Surface Science

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

Fabrication of BiOBr nanosheets@TiO2 nanobelts p–n junction

photocatalysts for enhanced visible-light activity
Yang Zhao a,1 , Xiang Huang a,b,1 , Xin Tan b , Tao Yu a,c,∗ , Xiangli Li d , Libin Yang e ,
Shucong Wang d
a
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China
b
School of Science, Tibet University, Lhasa 850000, PR China
c
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, PR China
d
School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, PR China
e
College of Chemical Engineering and Materials Science, Tianjin University of Science & Technology, Tianjin Key Laboratory of Marine Resources and
Chemistry, Tianjin 300457, China

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

Article history: The construction of p–n junction structure is a smart strategy for improving the photocatalytic
Received 26 October 2015 activity, since p–n junctions can inhibit the recombination of photo-induced charges. Herein, BiOBr
Received in revised form nanosheets@TiO2 nanobelts p–n junction photocatalysts were prepared by assembling BiOBr nanosheets
24 December 2015
on the surface of TiO2 nanobelts via a hydrothermal route followed by a co-precipitation process.
Accepted 26 December 2015
BiOBr@TiO2 p–n junction photocatalysts exhibited enhanced photocatalytic activity in photocatalytic
Available online 4 January 2016
H2 production over water splitting and photodegradation of Rhodamine B (RhB) under visible light irra-
diation. Mott–Schottky plots confirmed the formation of p–n junctions in the interface of BiOBr and TiO2 .
Keywords:
Photocatalysis
The enhanced photocatalytic performance can be ascribed to the 1D nanostructure and the formation of
p–n junction p–n junctions. This work shows a potential application of low cost BiOBr as a substitute for noble metals
Water splitting in photocatalytic H2 production under visible light irradiation.
1D nanostructure © 2016 Elsevier B.V. All rights reserved.
Heterostructure

1. Introduction surface, both visible-light activity and the separation efficiency of

Titanium dioxide (TiO2 ), one of the most useful semiconductor
materials, has been widely studied for photocatalytic application
due to its advantages, such as a suitable band gap for redox
reactions, high chemical stability, low cost, and non-toxicity [1].
However, there are two bottlenecks hindering the applications of
TiO2 as photocatalysts. One is high recombination rate of the photo-
induced electron–hole pairs, and the other is that pure TiO2 can
hardly absorb the visible light due to its wide band gap [1]. To date,
many strategies have been developed to solve the above problem.
An effective alternative is to couple TiO2 with narrow bad gap semi-
conductor or metal to form p–n junctions, Schottky junctions, and
band-structure matching [2,3]. Based on the interface engineer-
ing with the attachment of visibly active photocatalyst on the TiO2
∗ Corresponding author at: School of Chemical Engineering and Technology,
Tianjin University, and Collaborative Innovation Center of Chemical Science and
Engineering (Tianjin), Tianjin 300072, PR China.
E-mail address: yutao@tju.edu.cn (T. Yu).
1
These authors contributed equally to this work.
photo-induced carriers can be improved.
Many semiconductor materials have been used as secondary
phase hybridized with TiO2 , such as CdS [4], CuO [5], NiO [6],
MoS2 [7,8], CeO2 [9], BiVO4 [10] and so on. In the last ten years,
Bismuth oxyhalides BiOX (X = Cl, Br, I) has became a promising pho-
tocatalyst due to its special layered structure with [Bi2 O2 ] slabs
interleaved by double slabs of halogen atoms along the [0 0 1] direc-
tion. The internal static electric fields between the [Bi2 O2 ]2+ and
anionic halogen layers are believed to improve the separation of
photo-induced electron–hole pairs [11]. Notably, BiOX is a p-type
semiconductor [12–14], and BiOBr and BiOI with the band gaps
of ∼2.7 eV and ∼1.7 respectively [11] have visible-light response.
Therefore, BiOX, especially BiOI and BiOBr, is an attractive pho-
tocatalyst that can couple with TiO2 to form p–n junction and
improve visible-light response. Recently, effort has been spent
in studying the hybrid photocatalyst of TiO2 with BiOCl [15–17],
BiOBr [17–19], and BiOI [12,13,17,20–25]. These reports mainly
focused on the hybrid of TiO2 nanoparticles with BiOX. However,
it is hard for TiO2 nanoparticles to control the coverage and dis-
tribution of the secondary phase on the surface, which would
restrict the diffusion of photo-induced carriers to the TiO2 surface

http://dx.doi.org/10.1016/j.apsusc.2015.12.249
0169-4332/© 2016 Elsevier B.V. All rights reserved.
210 Y. Zhao et al. / Applied Surface Science 365 (2016) 209–217
[3]. Additionally, particle-like photocatalyst is inconvenient for
recycling. One-dimensional (1D) nanostructures, such as nanobelts,
nanorods, nanowires [7–9,26–33] and nanotubes [34,35], have
attracted tremendous attention because of their specific morphol-
ogy and novel properties. In comparison with nanoparticles, 1D
nanostructure can supply relatively large surface area for assem-
bling various secondary phase materials and transport charge
carriers rapidly along the axial direction [3].
Herein, we report the fabrication of p–n heterostructure BiOBr-
TiO2 photocatalysts (BiOBr@TiO2 ) by a simple co-precipitation
method. Firstly, TiO2 nanobelts were prepared via a typical hydro-
thermal route. Then BiOBr nanosheets were coupled on the surface
of TiO2 nanobelts. BiOBr@TiO2 was firstly applied to photocatalytic
H2 production over water splitting under visible light irradiation.
In addition, BiOBr@TiO2 exhibited excellent photocatalytic activity
in the photodegradation of RhB.
2. Experimental
2.1. Preparation of TiO2 nanobelts and BiOBr@TiO2
heterostructures
The chemicals used in this work were of analytical reagent
grade. The TiO2 nanobelts were synthesized via a typical hydro-
thermal method. Typically, 0.4 g of P25 was added in 40 mL of 10 M
NaOH aqueous solution under continuous stirring for 30 min. Then
the mixture was poured into a Teflon-lined stainless steel auto-
clave (50 mL volume). The autoclave was maintained at 180 ◦ C for
48 h and then cooled to room temperature naturally. The obtained
powder was washed with deionized water several times, followed
by an immersion process in 0.1 M of HCl aqueous solution for 24 h.
After that, the wet products were washed with deionized water to
pH 7, and then dried at 80 ◦ C over night. Finally, the TiO2 nanobelts
were obtained by heat treatment for 2 h at 600 ◦ C.
BiOBr@TiO2 nanobelt heterostructures at various mole ratios
of 0.5:1, 1:1 and 1.5:1 (note as BiOBr@TiO2 -0.5, BiOBr@TiO2 -
1, BiOBr@TiO2 -1.5) were prepared by a simple co-precipitation
method. In a typical procedure, an appropriate amount of KBr
was dissolved in 20 mL deionized water. Meanwhile, a stoichio-
metric amount of Bi(NO3 )3 ·5H2 O was added to 20 mL deionized
water to form a white suspension S1. Then 40 mg as-prepared TiO2
nanobelts were dispersed into the KBr solution under magnetic stir-
ring to form suspension S2. The suspension S2 was slowly poured
into the suspension S1. After vigorous stirring for 30 min, the
resulting precipitate was collected by centrifugation and washed
thoroughly with deionized water and ethanol. Finally, BiOBr@TiO2
heterostructures were obtained after dried at 60 ◦ C. For compar-
ison, pure BiOBr nanosheets were synthesized under the same
conditions in the absence of TiO2 nanobelts.
2.2. Characterization
The crystal structure of the products was identified by X-ray
diffraction (XRD, Rigaku D/MAX-2500) with Cu K˛ radiation. The
Raman spectra were recorded using a DXR Microscope Raman
spectrometer with a laser excitation of 532 nm at room temper-
ature. X-ray photoelectron spectroscopy (XPS) was employed for
the measurement of composition and chemical states of the sam-
ples. The morphology of the samples was observed using field
emission scanning electron microscope (FESEM, FEI Nanosem 430).
TEM images were conducted on a Tecnai G2 F20 transmission
electron microscope with an accelerating voltage of 200 kV. The
specific surface areas of the samples were measured and calcu-
lated by a BET apparatus (Quantachrome Autosorb iQ). The UV–vis
diffuse reflectance spectra were measured on a Shimadzu UV-2550
spectrophotometer using BaSO4 as a reference in the wavelength
of 200–800 nm. The photoluminescence (PL) spectra were acquired
at room temperature with an F-4600 fluorescence spectrometer
under the ultraviolet excitation of 260 nm.
2.3. Photocatalytic tests
The photodegradation of RhB under monochromatic visible-
light irradiation ( = 420 nm) was conducted to evaluate the
photocatalytic properties of the BiOBr@TiO2 nanobelt heterostruc-
tures. A 300 W Xe lamp (HXS-F/UV 300, Beijing NBet Technology
Co., Ltd) was used as light source. In each experiment, 50 mg of
photocatalyst powder was dispersed in 50 mL of 20 mg L−1 RhB
solution. Then, the suspensions were kept in the dark for 0.5 h with
continuous stirring before irradiation. During the photodegrada-
tion, the light intensity was maintained at about 100 mW cm−2 .
The concentration variation of RhB was monitored by a UV–vis
spectrophotometer (T6, Beijing Purkinje General Instrument Co.,
Ltd). For comparison, physically-mixed TiO2 nanobelts/BiOBr
nanosheets were employed for the photodegradation of RhB under
the same experimental condition.
In addition, H2 evolution from water splitting was performed
with ethylene glycol as sacrificial agent. 0.08 g of photocatalyst was
dispersed in the 80 mL aqueous solution. Before irradiation, the sys-
tem was bubbled with N2 for 30 min to remove the air inside. The
amount of H2 evolution was determined on a gas chromatograph
(GC-2014, Shimadzu, Tokyo).
2.4. Photoelectrochemical measurements
Photoelectrochemical properties of the as-prepared samples
were evaluated by a standard three-electrode configuration using
an electrochemical workstation (CHI660E, Shanghai Chenhua,
China). 1 M of Na2 SO4 solution was used as the supporting
electrolyte. The working electrode was prepared by depositing
photocatalyst powders on 1.0 cm × 1.0 cm fluoride-tin oxide (FTO)
glass. A saturated calomel electrode (SCE) and platinum wire
counter electrode (˚ 0.5 mm × 37 mm) were employed as the ref-
erence and counter electrodes, respectively.
3. Results and discussion
Fig. 1 shows the XRD patterns of pure BiOBr, TiO2 nanobelts,
BiOBr@TiO2 -0.5, BiOBr@TiO2 -1 and BiOBr@TiO2 -1.5. The corre-
sponding XRD of TiO2 nanobelts shows a mixed phase of TiO2
(B) and anatase. It can be observed from Fig. 1A(a) that TiO2 (B)
is the main phase having three major diffraction peaks at 14.19◦ ,
24.93◦ and 28.61◦ (JCPDS Card No.46-1237). Some weak response
peaks at 25.28◦ , 37.80◦ and 48.04◦ can be identified as the tetragonal
anatase phase (corresponding to JCPDS Card No. 21-1272). TiO2 (B),
TiO2 anatase and tetragonal BiOBr phases appear in the BiOBr@TiO2
nanobelt heterostructures, indicating the successful coupling of the
BiOBr nanosheets onto the TiO2 nanobelt surfaces. More specially,
the diffraction peaks of BiOBr are intensified gradually with the
loading of BiOBr increasing. In addition, anatase phase begins to
disappear from BiOBr@TiO2 -1, which can be attributed to the small
quantity of anatase and the coverage of the BiOBr nanosheets. As
shown in Fig. 1B(a), two peaks at 24.93◦ and 25.28◦ can be assigned
to the plane (1 1 0) of TiO2 (B) and the plane (1 0 1) of anatase
respectively, confirming the mixed phase of TiO2 nanobelts. Careful
observation from Fig. 1B shows that the two diffraction peaks are
converted gradually into one peak and shift slightly to the larger
value of the diffraction angle from curve a to curve e, because the
peaks ascribed to TiO2 (B) and anatase are weakened, while the
peak ascribed to the plane (1 0 1) of BiOBr at 25.16◦ (JCPDS Card No.
09-0393) [36] is intensified with the increase of BiOBr.
 Y. Zhao et al. / Applied Surface Science 365 (2016) 209–217
Fig. 1. XRD patterns of samples (a) pure TiO2 nanobelts, (b) BiOBr@TiO2 -0.5 (c) BiOBr@TiO2 -1, (d) BiOBr@TiO2 -1.5, and (e) pure BiOBr.
Fig. 2. Raman spectra of TiO2 nanobelts, pure BiOBr and BiOBr@TiO2 -1.
Fig. 2 shows Raman spectra of the as-prepared TiO2 nanobelts,
BiOBr and BiOBr@TiO2 -1. The bands at 125, 247, 254, 297, 370, 411,
437, and 471 cm−1 are assigned to TiO2 (B) [32,37,38]. The band
around 145 cm−1 is attributed to the B1g vibration of anatase [38].
The above analysis shows that the as-prepared TiO2 nanobelts are of
mixed phase of anatase and TiO2 (B), which is well accordant with
XRD results. Carefully observation on the curve of BiOBr@TiO2 -1
can find that the peak around 150 cm−1 is asymmetric and shifts
to the band position of pure BiOBr, further confirming that BiOBr is
successfully introduced on the surface of the TiO2 nanobelts.
XPS measurements were performed to explore the composi-
tion and elemental valence state of the BiOBr@TiO2 . As shown in
Fig. 3A, the survey spectrum of BiOBr@TiO2 -1 shows the existence
of Ti, Bi, Br, O and C in the heterostructure. The peak for C 1s at
284.8 eV is ascribed to adventitious carbon from the XPS instru-
ment. In Fig. 3B, two peaks at the binding energy of 159.3 eV and
164.6 eV for pure BiOBr are assigned to Bi 4f7/2 and Bi 4f5/2 , respec-
tively. However, the Bi 4f7/2 and Bi 4f5/2 peaks for BiOBr@TiO2 -1
have a slight shift to low binding energy, which can be ascribed to
the strong chemical bonding between BiOBr and TiO2 [16,18,19]. As
for the high-resolution spectra of Br 3d, the peaks located at 68.1 eV
and 69.1 eV (Fig. 3C) are ascribed to Br 3d5/2 and Br 3d3/2 respec-
tively, corresponding to Br− [39,40]. The two symmetric peaks for
TiO2 nanobelts located at 458.5 eV and 464.2 eV are assigned to Ti
2p3/2 and Ti 2p1/2 , indicating that Ti in the sample is in the form of
Ti4+ [23,24,41]. As for BiOBr@TiO2 -1, the peak of Ti 2p1/2 (Fig. 3D)
has a broad bump due to the partial overlap between Ti 2p1/2 at
464.4 eV and Bi 4d3/2 at 466.3 eV. The XPS results further confirm
the coexistence of TiO2 and BiOBr in the BiOBr@TiO2 heterostruc-
ture, and the BiOBr nanosheets were introduced on the surface of
TiO2 nanobelts through chemical bond rather than a simple mixture
of the two materials.
Fig. 4 presents the corresponding SEM images of pure
TiO2 nanobelts, pure BiOBr, and BiOBr@TiO2 heterostructures,
211
respectively. As shown in Fig. 4A, the as-prepared TiO2 nanobelts
are 50–200 nm wide, about 40 nm thick and of several micrometers
in length. Furthermore, it can be seen clearly that the surface of the
TiO2 nanobelts are smooth. Fig. 4 B is the typical SEM image of BiOBr
synthesized by the same route in the absence of TiO2 nanobelts.
The pure BiOBr exhibits flower-like 3D hierarchical structures
with an average diameter of ca. 1 ␮m, having radially grown
nanoplates which stacked and intercrossed with one another. After
co-precipitation procedure, the TiO2 nanobelts are decorated by
numerous thin BiOBr nanosheets and remain 1D nanostructure, as
shown in Fig. 4C–E. When the mass ratio of BiOBr to TiO2 was 0.5,
the density of BiOBr nanosheets on the TiO2 nanobelts was low,
so the smooth surface of TiO2 nanobelts still can be observed in
Fig. 4C. As the mass ratio was increased to 1, the density of the
nanosheets on the surface of TiO2 nanobelts increased significantly.
In particular, the nanosheets were distributed uniformly without
aggregation, and the belt-like morphology was changed to be cylin-
drical shape, as shown in Fig. 4D. With the mass ratio was further
increased to 1.5, the petal-like BiOBr nanosheets can be observed,
as shown in Fig. 4E. A careful observation reveals that BiOBr@TiO2 -
1.5 has a larger size of diameter (about 900 nm) than BiOBr@TiO2 -1
(about 500 nm), indicating more BiOBr nanosheets covered on the
surface of TiO2 nanobelts.
Fig. 5A and B shows the typical TEM images of BiOBr@TiO2 -1.
BiOBr nanosheets still cover the TiO2 nanobelts after ultrasonic
dispersion, confirming the stable combination between BiOBr and
TiO2 . The diameter of TiO2 nanobelts in Fig. 5A and B is about 65 nm
and 180 nm respectively, which agrees well with the results of SEM.
From the HRTEM images in Fig. 5C and D, the lattice fringes of BiOBr
nanosheets and TiO2 nanobelts can be seen clearly, suggesting the
well-defined crystal structure. The fringes with the lattice spacing
of 0.277 nm correspond to the (1 1 0) plane of BiOBr. Combining the
above results and the corresponding FFT pattern in Fig. 4D inset,
the top and bottom surfaces of the BiOBr nanosheets are indenti-
fied as {0 0 1} facets. The crystal structure of the mixed-phase TiO2
nanobelts can be confirmed in Fig. 5C. Two different fringes are
observed in TiO2 region. The main lattice spacing of ca. 0.506 nm
matches well with the (2 0 1) plane of TiO2 (B). The other fringes
with the spacing of 0.352 nm are ascribed to the (1 0 1) plane of
anatase phase. Interestingly, cross fringes occur in the interface of
BiOBr and TiO2 (Fig. 5D), indicating the well combination of the
two materials. In addition, the energy dispersive X-ray (EDX) ele-
mental mappings of Ti (Fig. 5H), Bi (Fig. 5I), Br (Fig. 5J), and O
(Fig. 5G) further confirm the formation of the heterostructures,
in which TiO2 nanobelts act as the core and BiOBr nanosheets are
well-distributed outside. EDX analysis of BiOBr@TiO2 -1 presented
in Fig. 5K indicates that the heterostructure is composed of Ti, Bi,
Br and O elements. The peaks of Cu and C are ascribed to the cop-
per net and the carbon film used in the EDX characterization. The
elemental content of BiOBr@TiO2 -1 is shown in Table S1.
212 Y. Zhao et al. / Applied Surface Science 365 (2016) 209–217
Fig. 3. XPS spectra of TiO2 nanobelts, pure BiOBr and BiOBr@TiO2 -1 (A) survey, (B) Bi 4f, (C) Br 3d, and (D) Ti 2p.
Fig. 6A shows the UV–vis diffuse reflectance spectra of the
pure BiOBr, TiO2 nanobelts and BiOBr@TiO2 heterostructures. Pure
TiO2 nanobelts have almost no absorbance in the visible light
range with an absorbance edge less than 400 nm, which can
be assigned to the intrinsic band-gap absorption. As for pure
BiOBr, red shift of the optical absorption edge is observed clearly.
The band gaps (Eg ) of the pure BiOBr and TiO2 nanobelts can
be evaluated by ˛(hv) = A(hv − Eg )n/2 , where ˛, h, v, Eg and A
are the absorption coefficient, Plank constant, light frequency,
band gap energy and a constant, respectively. Among them, n
depends on the characteristics of the transition in a semicon-
ductor. The estimated band gaps are about 2.75 eV and 3.02 eV
for pure BiOBr and TiO2 nanobelts (Fig. 6B), respectively, which
is close to the previous report [11,27,38]. Further observation
from Fig. 6A shows that the absorption edges of BiOBr@TiO2
heterostructures lie ca. 420 nm–430 nm, and have a continuous
red-shift with the increase of the BiOBr nanosheets grown on TiO2
nanobelts.
The photocatalytic activity of the BiOBr@TiO2 heterostructures
was evaluated by the photodegradation of RhB under visible
light irradiation. Considering that RhB itself with the maximum
absorption wavelength of 553 nm can absorb visible light and its
degradation can be initiated from the excited dye [42], a monochro-
matic visible light ( = 420 nm) was selected to eliminate the dye
sensitization effect since it has a minimal spectral overlap with
RhB. As shown in Fig. S1, RhB over BiOBr@TiO2 heterostructures
can be completely degraded only in 10 min under visible light
irradiation with an ultraviolet cutoff filter ( ≥ 420 nm), while it
needs at least 40 min under monochromatic light ( = 420 nm) in
Fig. 7A, confirming monochromatic light irradiation is favorable
for the elimination of dye sensitization effect. Additionally, blank
test indicates that the exposure of RhB without photocatalysts
to visible light doesn’t stimulate self-photodegradation. Fig. 7A
shows the variation in RhB concentration over the pure BiOBr,
BiOBr@TiO2 heterostructures and BiOBr + TiO2 (physical mixture)
under monochromatic light ( = 420 nm). The photodegradation
activity of the pure TiO2 nanobelts was negligible due to the wide
band gap. Clearly, the sample TiO2 + BiOBr (physically-mixed TiO2
nanobelts and BiOBr nanosheets) exhibits the lowest photocat-
alytic performance with the degradation efficiency of 34.1% in
40 min, confirming the p–n junction effect. Moreover, the degra-
dation rates of RhB over the BiOBr@TiO2 heterostructures are
higher than that over the pure BiOBr. Since the specific surface
area of the pure BiOBr is similar to those of BiOBr@TiO2 het-
erostructures (Fig. S2), we believe that the enhanced photocatalytic
activities of the BiOBr@TiO2 heterostructures are attributed to
the p–n junction effect rather than surface area. It is worth not-
ing that BiOBr amount in the heterostructures has an influence
on the photodegradation of RhB. When BiOBr@TiO2 -0.5 was used
as photocatalyst under monochromatic light ( = 420 nm), 84%
of RhB can be degraded in 40 min; while the degradation effi-
ciency of RhB was increased to 92.8% over BiOBr@TiO2 -1 under
the same condition. This can be attributed to two major rea-
sons. One is that more BiOBr nanosheets grown on the surface
of TiO2 are favorable for the absorption of visible light; the
other is that the formation of more p–n junctions in BiOBr@TiO2 -
1 facilitates the separation of photo-generated electrons and
holes, which leads to the enhanced photocatalytic activity. How-
ever, the degradation efficiency of RhB was decreased to 86.8%
when BiOBr amount was continuously increased (BiOBr@TiO2 -
1.5). The above results indicate that there is an optimum amount
of BiOBr in the heterostructures. Excess BiOBr amount can
also decrease the photocatalytic activity, because excess BiOBr
nanosheets grown on the surface of TiO2 nanobelts may act as
the recombination center of photo-induced carriers, resulting in
the rapid recombination of charges. To eliminate the adsorption
effect, the pseudo-first order model expressed by ln (C0 /C) = kt
was applied to the evaluation of the degradation rate, as shown
in Fig. 7B. The k values of the as-prepared photocatalysts are
in the order of BiOBr@TiO2 -1 (k = 0.061 min−1 ) > BiOBr@TiO2 -1.5
(k = 0.048 min−1 ) > BiOBr@TiO2 -0.5 (k = 0.044 min−1 ) > pure BiOBr
(k = 0.033 min−1 ) > BiOBr + TiO2 (k = 0.009 min−1 ).
 Y. Zhao et al. / Applied Surface Science 365 (2016) 209–217
Fig. 4. SEM images of (A) pure TiO2 nanobelts, (B) pure BiOBr, (C) BiOBr@TiO2 -0.5, (D) BiOBr@TiO2 -1, and (E) BiOBr@TiO2 -1.5.
Active species trapping experiments were carried out to inves-
tigate the photodegradation process of RhB. As shown in Fig. S3,
the RhB degradation was significantly suppressed by the addition
of benzoquinone (BQ, a ·O− 2 scavenger) [39,43]. However, when
EDTA (a hole scavenger) [39,43] and AgNO3 (a electron scavenger)
[19,39] were added, there was no apparent effect on the degra-
dation process. Additionally, trapping ·OH with 2-butyl alcohol
exhibited much weaker inhibition to the RhB photodegradation
than trapping ·O− −
2 . Therefore, it can be deduced that ·O2 was the
dominative active species for the RhB photodegradation.
The photocatalytic H2 -generation activity was measured to
evaluate the as-prepared catalysts under visible light irradiation
( ≥ 420 nm). It can be seen from Fig. 8 that TiO2 nanobelts show
negligible H2 -generation activity due to the poor visible-light
response. Additionally, the H2 -production of pure BiOBr is slight.
However, the H2 evolution over the BiOBr@TiO2 heterostructures
was significantly enhanced. Especially, there is an optimal ratio
of BiOBr to TiO2 in terms of H2 production. The BiOBr@TiO2 -1
exhibits highest H2 -generation activity up to 122 ␮mol−1 g−1 h−1 ,
which is 2-fold of BiOBr@TiO2 -0.5 and BiOBr@TiO2 -1.5. The results
are similar to the photodegradation of RhB. This is because that
low loading of BiOBr couldn’t absorb sufficient visible light, while
excess loading of BiOBr resulted in the rapid recombination of
213
electrons and holes. The photodegradation RhB and photocat-
alytic H2 evolution indicated that BiOBr@TiO2 heterostructures
possessed excellent activity in both photo-oxidation and photo-
reduction reactions.
It is well-established that BiOBr is a p-type semiconductor
[12–14] and TiO2 is an n-type semiconductor [1,12,13], which was
further confirmed by the Mott–Schottky plots in Fig. S4. As shown in
Fig. S4, the BiOBr nanosheets show a negative slope, while the TiO2
nanobelts show a positive slope, indicating that BiOBr is a p-type
semiconductor and TiO2 is an n-type semiconductor. When p-type
BiOBr nanosheets grew on the surface of n-type TiO2 nanobelts, a
number of p–n junctions would form at the interface. Fig. 9A shows
an inverted “V-shape” in the Mott–Schottky plots of BiOBr@TiO2 -1.
The co-existence positive and negative slopes with similar values
confirmed the formation of p–n junctions [44,45]. The valence band
(VB) edge positions of the pure BiOBr and TiO2 nanobelts deter-
mined by the XPS VB spectra were 1.96 eV and 2.8 eV respectively,
as shown in Fig. 9B. Therefore, the conduction band (CB) edges of
the as-prepared BiOBr and TiO2 can be calculated to be −0.79 eV
and −0.22 eV according to the equation ECB = EVB − Eg , where Eg is
the band gap energy obtained by UV–vis diffuse reflection spectra
(Fig. 6B). The p–n junction band structure and the possible charge
separation mechanism are illustrated in Fig. 9C and D. TiO2 is a
214 Y. Zhao et al. / Applied Surface Science 365 (2016) 209–217

Fig. 5. (A and B) Low-magnification TEM images of BiOBr@TiO2 -1, (C and D) HRTEM images of the designated square parts in A and B, (E–J) EDX elemental mappings of
BiOBr@TiO2 -1, and (K) EDX analysis of BiOBr@TiO2 -1.

Fig. 6. (A) UV–vis diffuse reflection spectra of pure BiOBr, TiO2 nanobelts and BiOBr@TiO2 heterostructures, and (B) (ahv)1/2 vs. photon energy.
 Y. Zhao et al. / Applied Surface Science 365 (2016) 209–217 215

Fig. 7. (A) Photocatalytic degradation efficiencies of RhB and (B) kinetics of RhB decolorization under visible light irradiation ( = 420 nm).

Fig. 8. Comparison of the photocatalytic hydrogen-generation activities of pure
BiOBr, TiO2 nanobelts, and BiOBr@TiO2 heterostructures under visible light irra-
diation ( ≥ 420 nm).
typical n-type semiconductor with Femi level located close to CB,
while BiOBr is a p-type semiconductor whose Femi level lies close
to VB, as shown in Fig. 9C. Before contact, the Femi level of BiOBr is
lower than that of TiO2 . Once p-type BiOBr and n-type TiO2 contact
each other, the Femi level difference between BiOBr and TiO2 causes
electron transfer from TiO2 to BiOBr until the Femi levels of BiOBr
and TiO2 reach an equilibrium [46–48]. As a consequence, the Femi
levels of BiOBr and TiO2 rise up and descend respectively, and an
inner electric field is established from n-TiO2 to p-BiOBr (Fig. 9D).
When the p–n junction photocatalysts were irradiated with visi-
ble light, the electrons were excited from the VB of BiOBr to its CB
because the BiOBr nanosheets with the band gap energy of 2.75 eV
can absorb visible light. Driven by the inner electric field, the photo-
induced electrons on the CB of p-BiOBr transferred to that of n-TiO2 ,
and holes remained on the VB of p-BiOBr. Therefore, photo-induced
carriers were effectively separated by the p–n junction and the
recombination of the electrons and holes was retarded, which was
beneficial to the photocatalytic activity.
To verify the above proposed mechanism, the photoluminesce-
nce (PL) emission spectra were measured under the ultraviolet
excitation of 260 nm. The higher the PL intensity, the higher recom-
bination rate of photo-generated electrons and holes. A comparison
of pure BiOBr nanosheets, TiO2 nanobelts and BiOBr@TiO2 -1 is
shown in Fig. 10A. It can be clearly seen that the emission

Fig. 9. (A) Mott–Schottky plots of BiOBr@TiO2 -1, (B) XPS valence-band spectra of pure BiOBr nanosheets and TiO2 nanobelts, and schematic illustrations for (C) the band
energy of BiOBr and TiO2 before contact and (D) the formation of p–n junction and the charge transfer and separation process under visible light irradiation.
216 Y. Zhao et al. / Applied Surface Science 365 (2016) 209–217
Fig. 10. (A) Photoluminescence (PL) spectra of pure BiOBr, TiO2 nanobelts and BiOBr@TiO2 -1.0 at room temperature with the excitation wavelength of 260 nm, and (B)
photocurrent responses of pure BiOBr, TiO2 nanobelts and BiOBr@TiO2 heterostructures in 0.1 M Na2 SO4 aqueous solution under visible light irradiation ( ≥ 420 nm).
intensity of BiOBr@TiO2 -1 is much lower than those of pure BiOBr
and TiO2 , suggesting that the recombination of photo-induced
electron–hole pairs is hampered. To further investigate the separa-
tion of electron–hole pairs, the transient photocurrent responses
of pure BiOBr, TiO2 + BiOBr, and three BiOBr@TiO2 heterostruc-
tures were measured under visible light irradiation ( ≥ 420 nm). As
shown in Fig. 10B, all the samples generate photocurrent promptly,
and BiOBr@TiO2 -1 exhibits the highest photocurrent intensity.
Carefully observation indicates that the photocurrent intensities
are in the order of TiO2 + BiOBr < BiOBr@TiO2 -0.5 < BiOBr@TiO2 -
1.5 ≈ pure BiOBr < BiOBr@TiO2 -1.0. It is not surprising that
TiO2 + BiOBr show the lowest photocurrent intensity due to the
intrinsic wide band gap of TiO2 , which is in accord with the result
of photodegradation RhB. When BiOBr nanosheets were deposited
on the surface of TiO2 nanobelts, the absorption capacity for visible
light was improved, which led to the enhanced photocurrent inten-
sities of BiOBr@TiO2 heterostructures. However, the photocurrent
of BiOBr@TiO2 -1.5 is weaker than that of BiOBr@TiO2 -1.0 probably
because excess BiOBr nanosheets would act as the recombination
centers, resulting in lower charge separation efficiency. To provide
additional evidence for the above mechanism, electrochemical
impedance spectroscopy (EIS) were carried out under dark con-
dition. It can be seen from Fig. S5 that the arc radii of the samples
are arranged similar to the trend of the photocurrent. BiOBr@TiO2 -
1.0 shows the smallest arc radius, which further demonstrates that
the BiOBr@TiO2 -1.0 electrode has a higher separation efficiency
of photo-generated electron–hole pairs and faster charge-transfer
than the other samples at the solid-liquid interface. Therefore,
the results confirm that the BiOBr@TiO2 heterostructures, espe-
cially BiOBr@TiO2 -1.0, can effectively inhibit the recombination of
photo-induced electron–hole pairs, which in turn leads to the high
photocurrent response and excellent activity in photodegradation
dyes and photocatalytic H2 production.
4. Conclusions
In summary, the BiOBr@TiO2 hybrid photocatalysts have been
successfully prepared with the growth of BiOBr nanosheets on the
surface of TiO2 nanobelts. According XRD, Ramam spectra and TEM,
the TiO2 nanobelts are of mixed phase of anatase and TiO2 (B).
Then the optimal BiOBr loading content was determined to be the
ratio of BiOBr to TiO2 1:1. Mott–Schottky plots indicated the for-
mation of p–n junctions at the interface of BiOBr nonasheets and
TiO2 nanobelts. Compared with the pure BiOBr, TiO2 nanobelts and
other BiOBr@TiO2 heterostructures, BiOBr@TiO2 -1.0 exhibited the
best photocatalytic performance for the degradation of RhB and
photocatalytic H2 production
over water splitting under visible light irradiation. It is believed
that the formation of p–n junctions could reduce the recombination
of photo-induced electron–hole pairs and that 1D TiO2 nanobelts
could supply abundant active sites for forming p–n junctions and
promote charge carriers separation.
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (21406164, 21466035), the National Key Basic
Research and Development Program of China (973 program, No.
2014CB239300, and 2012CB720100), Research Fund for the Doc-
toral Program of Higher Education of China (Nos. 20110032110037,
20130032120019).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apsusc.2015.12.
249.
References
[1] J. Schneider, M. Matsuoka, M. Takeuchi, J.L. Zhang, Y. Horiuchi, M. Anpo, D.W.
Bahnemann, Understanding TiO2 photocatalysis: mechanisms and materials,
Chem. Rev. 114 (2014) 9919–9986.
[2] Y.Q. Qu, X.F. Duan, Progress, challenge and perspective of heterogeneous
photocatalysts, Chem. Soc. Rev. 42 (2013) 2568–2580.
[3] J. Tian, Z.H. Zhao, A. Kumar, R.I. Boughton, H. Liu, Recent progress in design,
synthesis, and applications of one-dimensional TiO2 nanostructured surface
heterostructures: a review, Chem. Soc. Rev. 43 (2014) 6920–6937.
[4] H. Tada, T. Mitsui, T. Kiyonaga, T. Akita, K. Tanaka, All-solid-state Z-scheme in
CdS–Au–TiO2 three-component nanojunction system, Nat. Mater. 5 (2006)
782–786.
[5] L. Zhao, T. Cui, Y.J. Li, B. Wang, J.H. Han, L. Han, Z.F. Liu, Efficient visible light
photocatalytic activity of p–n junction CuO/TiO2 loaded on natural zeolite,
RSC Adv. 5 (2015) 64495–64502.
[6] M.G. Wang, Y.M. Hu, J. Han, R. Guo, H.X. Xiong, Y.D. Yin, TiO2 /NiO hybrid
shells: p–n junction photocatalysts with enhanced activity under visible light,
J. Mater. Chem. A 3 (2015) 20727–20735.
[7] W.J. Zhou, Z.Y. Yin, Y.P. Du, X. Huang, Z.Y. Zeng, Z.X. Fan, H. Liu, J.Y. Wang, H.
Zhang, Synthesis of few-layer MoS2 nanosheet-coated TiO2 nanobelt
heterostructures for enhanced photocatalytic activities, Small 9 (2013)
140–147.
[8] M.L. Mao, L. Mei, D. Guo, L.C. Wu, D. Zhang, Q.H. Li, T.H. Wang, High
electrochemical performance based on the TiO2 nanobelt@few-layered MoS2
structure for lithium-ion batteries, Nanoscale 6 (2014) 12350–12353.
[9] J. Tian, Y.H. Sang, Z.H. Zhao, W.J. Zhou, D.Z. Wang, X.L. Kang, H. Liu, J.Y. Wang,
S.W. Chen, H.Q. Cai, H. Huang, Enhanced photocatalytic performances of
CeO2 /TiO2 nanobelt heterostructures, Small 9 (2013) 3864–3872.
[10] Y. Hu, D.Z. Li, Y. Zheng, W. Chen, Y.H. He, Y. Shao, X.Z. Fu, G.C. Xiao, BiVO4 /TiO2
nanocrystalline heterostructure: a wide spectrum responsive photocatalyst
towards the highly efficient decomposition of gaseous benzene, Appl. Catal. B:
Environ. 104 (2011) 30–36.
 Y. Zhao et al. / Applied Surface Science 365 (2016) 209–217
[11] H.F. Cheng, B.B. Huang, Y. Dai, Engineering BiOX (X = Cl, Br, I) nanostructures
for highly efficient photocatalytic applications, Nanoscale 6 (2014)
2009–2026.
[12] G.P. Dai, J.G. Yu, G. Liu, Synthesis and enhanced visible-light
photoelectrocatalytic activity of p–n junction BiOI/TiO2 nanotube arrays, J.
Phys. Chem. C 115 (2011) 7339–7346.
[13] J.Q. Liu, L.L. Ruan, S.B. Adeloju, Y.C. Wu, BiOI/TiO2 nanotube arrays, a unique
flake-tube structured p–n junction with remarkable visible-light
photoelectrocatalytic performance and stability, Dalton Trans. 43 (2014)
1706–1715.
[14] D.F. Hou, X.L. Hu, P. Hu, W. Zhang, M.F. Zhang, Y.H. Huang, Bi4 Ti3 O12
nanofibers-BiOI nanosheets p–n junction: facile synthesis and
enhanced visible-light photocatalytic activity, Nanoscale 5 (2013)
9764–9772.
[15] W.Q. Fan, X.Q. Yu, S.Y. Song, H.Y. Bai, C. Zhang, D. Yan, C.B. Liu, Q. Wang, W.D.
Shi, Fabrication of TiO2 –BiOCl double-layer nanostructure arrays for
photoelectrochemical water splitting, CrystEngComm 16 (2014)
820–825.
[16] F.F. Duo, Y.W. Wang, C.M. Fan, X.M. Mao, X.C. Zhang, Y.F. Wang, J.X. Liu, Low
temperature one-step synthesis of rutile TiO2 /BiOCl composites with
enhanced photocatalytic activity, Mater. Charact. 99 (2015) 8–16.
[17] J. Yang, X.X. Wang, X.W. Lv, X.R. Xu, Y.J. Mi, J.L. Zhao, Preparation and
photocatalytic activity of BiOX-TiO2 composite films (X = Cl, Br, I), Ceram. Int.
40 (2014) 8607–8611.
[18] X.X. Wei, H.T. Cui, S.Q. Guo, L.F. Zhao, W. Li, Hybrid BiOBr-TiO2
nanocomposites with high visible light photocatalytic activity for water
treatment, J. Hazard. Mater. 263 (2013) 650–658.
[19] X.J. Wang, W.Y. Yang, F.T. Li, J. Zhao, R.H. Liu, S.J. Liu, B. Li, Construction of
amorphous TiO2 /BiOBr heterojunctions via facets coupling for enhanced
photocatalytic activity, J. Hazard. Mater. 292 (2015) 126–136.
[20] X. Zhang, L.Z. Zhang, T.F. Xie, D.J. Wang, Low-temperature synthesis and high
visible-light-induced photocatalytic activity of BiOI/TiO2 heterostructures, J.
Phys. Chem. C 113 (2009) 7371–7378.
[21] Y.Y. Li, J.S. Wang, B. Liu, L.Y. Dang, H.C. Yao, Z.J. Li, BiOI-sensitized TiO2 in
phenol degradation: a novel efficient semiconductor sensitizer, Chem. Phys.
Lett. 508 (2011) 102–106.
[22] Z. Liu, X.X. Xu, J.Z. Fang, X.M. Zhu, J.H. Chu, B.J. Li, Microemulsion synthesis,
characterization of bismuth oxyiodine/titanium dioxide hybrid nanoparticles
with outstanding photocatalytic performance under visible light irradiation,
Appl. Surf. Sci. 258 (2012) 3771–3778.
[23] D.Y. Wu, H.Y. Wang, C.L. Li, J. Xia, X.J. Song, W.S. Huang, Photocatalytic
self-cleaning properties of cotton fabrics functionalized with p-BiOI/n-TiO2
heterojunction, Surf. Coat. Technol. 258 (2014) 672–676.
[24] C.X. Liao, Z.J. Ma, G.P. Dong, J.R. Qiu, BiOI nanosheets decorated TiO2
nanofiber: tailoring water purification performance of photocatalyst in
structural and photo-responsivity aspects, Appl. Surf. Sci. 314 (2014)
481–489.
[25] L.Y. Wang, W.A. Daoud, BiOI/TiO2 -nanorod array heterojunction solar cell:
growth, charge transport kinetics and photoelectrochemical properties, Appl.
Surf. Sci. 324 (2015) 532–537.
[26] X.D. Wang, Z.D. Li, J. Shi, Y.H. Yu, One-dimensional titanium dioxide
nanomaterials: nanowires, nanorods, and nanobelts, Chem. Rev. 114 (2014)
9346–9384.
[27] Z.H. Zhao, J. Tian, Y.H. Sang, A. Cabot, H. Liu, Structure, synthesis, and
applications of TiO2 nanobelts, Adv Mater. 27 (2015) 2557–2582.
[28] I.S. Cho, Z.B. Chen, A.J. Forman, D.R. Kim, P.M. Rao, T.F. Jaramillo, X.L. Zheng,
Branched TiO2 nanorods for photoelectrochemical hydrogen production,
Nano Lett. 11 (2011) 4978–4984.
[29] J.Z. Chen, H.B. Yang, J.W. Miao, H.-Y. Wang, B. Liu, Thermodynamically driven
one-dimensional evolution of anatase TiO2 nanorods: one-step hydrothermal
synthesis for emerging intrinsic superiority of dimensionality, J. Am. Chem.
Soc. 136 (2014) 15310–15318.
217
[30] Y.J. Hwang, C. Hahn, B. Liu, P.D. Yang, Photoelectrochemical properties of TiO2
nanowire arrays: a study of the dependence on length and atomic layer
deposition coating, ACS Nano 6 (2012) 5060–5069.
[31] J.H. Yi, L.L. Huang, H.J. Wang, H. Yu, F. Peng, AgI/TiO2 nanobelts monolithic
catalyst with enhanced visible light photocatalytic activity, J. Hazard. Mater.
284 (2015) 207–214.
[32] D. Sarkar, K.K. Chattopadhyay, Branch density-controlled synthesis of
hierarchical TiO2 nanobelt and tunable three-step electron transfer for
enhanced photocatalytic property, ACS Appl. Mater. Interfaces 6 (2014)
10044–10059.
[33] Y.H. Sang, Z.H. Zhao, J. Tian, P. Hao, H.D. Jiang, H. Liu, J.P. Claverie, Enhanced
photocatalytic property of reduced graphene oxide/TiO2 nanobelt surface
heterostructures constructed by an in situ photochemical reduction method,
Small 10 (2014) 3775–3782.
[34] K. Lee, A. Mazare, P. Schmuki, One-dimensional titanium dioxide
nanomaterials: nanotubes, Chem. Rev. 114 (2014) 9385–9454.
[35] P. Roy, S. Berger, P. Schmuki, TiO2 nanotubes: synthesis and applications,
Angew. Chem. Int. Ed. 50 (2011) 2904–2939.
[36] R. Li, X.Y. Gao, C.M. Fan, X.C. Zhang, Y.W. Wang, Y.F. Wang, A facile approach
for the tunable fabrication of BiOBr photocatalysts with high activity and
stability, Appl. Surf. Sci. 355 (2015) 1075–1082.
[37] J. Dai, J. Yang, X.H. Wang, L. Zhang, Y.J. Li, Enhanced visible-light
photocatalytic activity for selective oxidation of amines into imines over
TiO2 (B)/anatase mixed-phase nanowires, Appl. Surf. Sci. 349 (2015) 343–352.
[38] W.J. Zhou, L.G. Gai, P.G. Hu, J.J. Cui, X.Y. Liu, D.Z. Wang, G.H. Li, H.D. Jiang, D.
Liu, H. Liu, J.Y. Wang, Phase transformation of TiO2 nanobelts and
TiO2 (B)/anatase interface heterostructure nanobelts with enhanced
photocatalytic activity, CrystEngComm 13 (2011) 6643–6649.
[39] Y.N. Huo, J. Zhang, M. Miao, Y. Jin, Solvothermal synthesis of flower-like BiOBr
microspheres with highly visible-light photocatalytic performances, Appl.
Catal. B: Environ. 111–112 (2012) 334–341.
[40] X.J. Shi, X. Chen, X.L. Chen, S.M. Zhou, S.Y. Lou, Y.Q. Wang, L. Yuan, PVP
assisted hydrothermal synthesis of BiOBr hierarchical nanostructures and
high photocatalytic capacity, Chem. Eng. J. 222 (2013) 120–127.
[41] J.Y. Zhang, F.X. Xiao, G.C. Xiao, B. Liu, Self-assembly of a Ag
nanoparticle-modified and graphene-wrapped TiO2 nanobelt ternary
heterostructure: surface charge tuning toward efficient photocatalysis,
Nanoscale 6 (2014) 11293–11302.
[42] S.Y. Baea, S.J. Kim, S.H. Lee, W.Y. Choi, Dye decolorization test for the activity
assessment of visible light photocatalysts: realities and limitations, Catal.
Today 224 (2014) 21–28.
[43] T.B. Li, G. Chen, C. Zhou, Z.Y. Shen, R.C. Jin, J.X. Sun, New photocatalyst
BiOCl/BiOI composites with highly enhanced visible light photocatalytic
performances, Dalton Trans. 40 (2011) 6751–6758.
[44] J.T. Li, F.K. Meng, S. Suri, W.Q. Ding, F.Q. Huang, N.Q. Wu,
Photoelectrochemical performance enhanced by a nickel oxide-hematite p–n
junction photoanode, Chem. Commun. 48 (2012) 8213–8215.
[45] F.K. Meng, J.T. Li, S.K. Cushing, M.J. Zhi, N.Q. Wu, Solar hydrogen generation by
nanoscale p–n junction of p-type molybdenum disulfide/n-type
nitrogen-doped reduced grapheme oxide, J. Am. Chem. Soc. 135 (2013)
10286–10289.
[46] J. Zhang, S.Z. Qiao, L.F. Qi, J.G. Yu, Fabrication of NiS modified CdS nanorod p–n
junction photocatalysts with enhanced visible-light photocatalytic
H2 -production activity, Phys. Chem. Chem. Phys. 15 (2013) 12088–12094.
[47] Y.B. Chen, Z.X. Qin, X.X. Wang, X. Guo, L.J. Guo, Noble-metal-free
Cu2 S-modified photocatalysts for enhanced photocatalytic hydrogen
production by forming nanoscale p–n junction structure, RSC Adv. 5 (2015)
18159–18166.
[48] W.Z. Wang, J. Wang, Z.Z. Wang, X.Z. Wei, L. Liu, Q.S. Ren, W.L. Gao, Y.J. Liang,
H.L. Shi, p–n junction CuO/BiVO4 heterogeneous nanostructures: synthesis
and highly efficient visible-light photocatalytic performance, Dalton Trans. 43
(2014) 6735–6743.