Solid State Sciences 105 (2020) 106288

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Solid State Sciences

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Facile construction of BiOBr/Bi2O2CO3 p-n heterojunction by precipitation

conversion at ambient temperature for charge transfer and
photocatalytic activity
Jun-jin Wang a, Xiao-Ya Zhai a, Guo-Ying Zhang a, b, *, Jing-Bo Zhang a, Yi-Fan Zhao a
a
College of Chemistry, Tianjin Normal University, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic-Organic
Hybrid Functional Material Chemistry, Ministry of Education, Tianjin, 300387, PR China
b
Shandong Provincial Key Laboratory of Clean Production of Fine Chemicals, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal
University, Jinan, 250014, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, an effective BiOBr/Bi2O2CO3 p-n heterojunction was established via a precipitation conversion
Bi2O2CO3 method at ambient temperature. The light response of the hybrid was broadened for 16 nm compared with that
BiOBr of Bi2O2CO3. More importantly, the charge transfer in BiOBr/Bi2O2CO3 heterojunction was greatly promoted as
p-n heterojunction
evidenced by photocurrent, ESI and PL results. So the photocatalytic ability of BiOBr/Bi2O2CO3 was greatly
Precipitation conversion
Photocatalysis
improved towards degradation of organic pollutants. The sample of Br amount of 0.094 wt% showed the optimal
Charge migration photoactivity for RhB degradation, with a rate constant k of 14.8 times as much as that of Bi2O2CO3. The reason
is ascribed to the established built-in electrical field and resulted band matching between BiOBr and Bi2O2CO3.
Based on the results, the migration mechanism of photoinduced charges at the interface of the heterojunction
was put forward. This work provides a useful perspective in design and fabrication of Bi(III)-based hetero­
structure with an enhanced photocatalytic activity.

1. Introduction masses of photoinduced carriers and resultantly benefit a longer

migration distance for the holes and electrons [13]. Besides, the inherent
Energy crisis and environmental deterioration are becoming the two layered structure of Bi-based photocatalysts enables them to generate a
concerned issues on a globle scale [1]. Heterogeneous photocatalysis large internal electric field, which could enhance the separation and
based on inorganic semiconductor has been considered as the preferred transfer efficiency of the photoinduced charges [14]. Bi2O2CO3 (BOC)
alternative to solve the problems due to its cost-effectiveness, low-­ belongs to Aurivillius-type oxide family with crystal structure stacked by
energy consumption and mild reaction conditions [2,3]. It is well known alternative [Bi2O2]2þ and CO23 sheets. The Bi–O polyhedron formed by
that TiO2 [4] and ZnO [5] have been extensively explored as the most bismuth and eight coordinated oxygen atoms presents large distortion
conventional photocatalysts. But their practical applications were due to the active lone-pair behavior of Bi3þ [15], which can result in
severely frustrated due to the defect of only UV-light response and the asymmetrical polarization effect and favors for the charge separation. By
rapid recombination of photogenerated charges. It is strongly expected far, BOC has been widely investigated as a safety photocatalyst for
to seek novel semiconductor photocatalysts with good eco-friendliness, degradation of harmful contaminants and great progress has been made
broadened light absorption and better carrier separation efficiency. by strategies of microstructure control [16,17] and hierarchical con­
Bismuth-based materials such as Bi2O3 [6], BiOIO3 [7], BiVO4 [8], struction [18]. However, for practical application, the photoactivity of
Bi2MoO6 [9], BiOX [10,11], and Bi4NbO8Cl [12] have drawn much BOC is needed to be further improved concerning the limited sunlight
attention in the photocatalytic field. In general, there is a strong hy­ capture and fast recombination of photoinduced carriers in a single
bridization between Bi 6s and O 2p orbitals in the conduction band and semiconductor.
valence band of Bi(III)-based compounds. It would decrease the effective The construction of BOC hybrids with oxide [19], sulfide [20] and

* Corresponding author. College of Chemistry, Tianjin Normal University, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key
Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin, 300387, PR China.
E-mail address: [email protected] (G.-Y. Zhang).

https://doi.org/10.1016/j.solidstatesciences.2020.106288
Received 13 March 2020; Received in revised form 7 May 2020; Accepted 12 May 2020
Available online 20 May 2020
1293-2558/© 2020 Elsevier Masson SAS. All rights reserved.
J.-j. Wang et al. Solid State Sciences 105 (2020) 106288

would make the synthesis on a large scale more difficult, so it is fasci­

nating to explore a more simplified and effective route to construct
BiOBr decorated BOC nanostructures.
Herein, a p-n type BiOBr/BOC nanocomposite was synthesized via a
facile precipitation conversion method for a short time of 50 min at
ambient temperature. The photocatalytic activity of the as-fabricated
BiOBr/BOC heterojunction was significantly boosted in the degrada­
tion of organic contaminates compared with that of BOC substrate. In
particular, the composite with a Br mass percentage of 0.094% has the
optimum catalytic efficiency for RhB degradation with a rate constant
14.8 folds as high as that of BOC. The excellent photocatalytic behavior
was interpreted by the accelerated charge migration as well as widened
light harvesting of the BiOBr/BOC heterojunction. According to the
measured active species and the band edge positions, the charge transfer
path and mechanism at the interface of BiOBr and BOC semiconductors
was put forward.

2. Experimental

2.1. Preparation

All the chemicals were of analytical grade and directly used without
any purification. The BiOBr/BOC composite was synthesized via a pre­
cipitation conversion method at room temperature. In brief, 1.0 mmol of
Bi(NO3)3⋅5H2O and 6.0 mmol of Na2CO3 were dissolved in 8.0 mL and
10.0 mL of deionized water, respectively. Then, the Na2CO3 solution was
added dropwise into Bi(NO3)3 precursor solution with magnetic stirring
for 20 min. Subsequently, a certain amount of NaBr was introduced into
the previous suspension. The mixture was treated with continuous
stirring for another 30 min at ambient temperature. Before drying at 60
�
C in air, the obtained solid was collected by centrifugation and washed
several times with deionized water and ethanol. For comparison, the
substrate and different BiOBr/BOC samples were prepared by regulating
the NaBr amount of 0, 0.02, 0.10, 0.18 and 0.26 mmol and marked as
BOC, BC-1, BC-2, BC-3 and BC-4, respectively.

2.2. Characterization

The phase structure of samples was monitored on a D8-Advance X-

ray diffraction (XRD, Bruker) with a Cu Ka radiation. The surface
property and composition were performed on an X-ray photoelectron
spectrometer (XPS, Thermo Fisher). The morphology were examined on
Fig. 1. XRD patterns of BOC, BiOBr, and series of BiOBr/BOC composites. a scanning electron microscope (FESEM, FEI, NOVA Nano SEM 230) and
the microstructure was acquired on a transmission electron microscope
(TEM, FEI Tecnai G2 F20). The Br content was measured with a Dionex
carbonaceous material [21] as well as ion doping [22] have been proved
IC2020 ion chromatography. The Brunauer Emmett Teller (BET) surface
to be effective strategies to elevate the photocatalytic activity. Espe­
area was tested by N2 adsorption-desorption isotherms at 77 K on a
cially, the p-n heterojunction is one of the most efficient ways to increase
Micromeritics ASAP2020 instrument. Photoluminescence (PL) was
the efficiency for charge separation and transfer owing to the formation
recorded on an F-4500 to monitor the charge separation. The diffuse
of built-in electric field and potential difference at the interface [23]. It
reflectance spectra (DRS) were obtained using a V-550/V-570 UV–vis
has been confirmed that the heterostructures of n-type BOC with p-type
spectrophotometer (JASCO). The radical signal was probed by an elec­
semiconductors such as Co3O4 [24], Ag2O [25] and BiOCl [26] could
tron spin resonance (ESR) spectrometer (JEOL JES-FA200) with a Xe
effectively improve the photoactivity of BOC. As another kind of Bi
lamp source.
(III)-based photocatalyst, BiOBr is one of p-type semiconductors and
sensitive to visible light with similar layered structure [27,28]. The
2.3. Photocatalytic degradation test
fabrication of BiOBr/BOC heterojunction is expected to promote the
migration of photoinduced carriers as well as enhance the utilization of
The photocatalytic behavior of the samples was evaluated by the
sunlight. Qiu’s group [29] and Cheng’s group [30] fabricated BiO­
degradation of organic contaminants. A 250 W Xe lamp served as the
Br/BOC composites via two-step methods, respectively. In their routes,
simulated sunlight source equipped with a cooling water system. In a
the BOC was needed to be firstly prepared by a hydrothermal process at
typical process, 5.0 mg of photocatalyst powder was dispersed into 10.0
160 � C for 10 h or by a CTAB-assisted solution reaction. In addition,
mL RhB solution of 1.0 � 10 5 M in a quartz tube. After magnetically
BiOBr/BOC nanosheets were also prepared by a 60 � C solid-state reac­
stirring in the dark-box for 30 min, an adsorption-desorption balance of
tion for a long time span of 3 days [15] and a one-step hydrothermal
the suspension was established and then the light source was turned on.
route at 180 � C for 16 h [31], respectively. Apparently, the reported
At given time intervals, one sample tube was taken out and the solid-
synthetic routes of BiOBr/BOC heterostructures were energy- and
liquid separation was immediately operated by centrifugation. The ab­
time-consumption and sometimes depended on a capping agent. These
sorption spectrum of the clear solution was monitored on a Shimadzu

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J.-j. Wang et al. Solid State Sciences 105 (2020) 106288

Fig. 2. XPS spectra of BOC and BC-3 samples: (a) survey, (b) Br 3 d, (c) Bi 4f, (d) O 1s and (e) C 1s; (f) EDS profile of the BC-3 composite.

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J.-j. Wang et al. Solid State Sciences 105 (2020) 106288

Fig. 3. (a) SEM image of BOC; (b) SEM image, (c) TEM image, (d) HRTEM images with SAED pattern in inset, and (e–g) EDX mapping of BC-3 sample, respectively.

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3. Results and discussion

3.1. Composition analysis

The powder XRD pattern provides information of crystal structure,

crystallinity and purity of the samples. Fig. 1a shows that the diffraction
pattern of BOC matches well with the phase structure of tetragonal
Bi2O2CO3 (JCPDS 41–1488). The sharp diffraction pattern indicates
excellent crystallinity of BOC synthesized at ambient temperature. With
the addition of NaBr from 0.02 to 0.26 mmol, the XRD patterns of BC-1
to BC-4 were almost identical with that of BOC and no obvious peaks of
BiOBr were detected. It may be ascribed to the extremely low content of
BiOBr, which has exceeded the detection limit of the XRD instrument. In
order to explore the transformation from BOC to BiOBr, contrast ex­
periments with more NaBr and different sequence of precipitant were
conducted. As shown in Fig. 1b, the BC-5 was obtained with a more NaBr
amount of 1.80 mmol, in which still no obvious BiOBr peak was detec­
ted. It was deduced that the BiOBr transformed from BOC was very few
due to the lower solubility of BOC than BiOBr. The inference was evi­
denced by the contrast experiment with exchanged addition order of
Na2CO3 and NaBr (1.80 mmol). When NaBr was first added into Bi
(NO3)3 solution, well-indexed BiOBr (JCPDS 78–0348) was obtained as
shown by the bottom XRD pattern in Fig. 1b. With the continued addi­
tion of Na2CO3, the final sample of BC-6 was assigned back to BOC
phase. The trace content of BiOBr in the composite was confirmed by IC
results, in which the Br percentage of BC-1 to BC-4 is 0.053%, 0.063%,
0.094% and 0.383%, respectively.
XPS measurement was conducted for the surface elemental analysis
of bare BOC and BC-3. In Fig. 2a, the survey XPS spectra indicate that the
Bi, O and C elements exist in both the two samples. However, a very
weak peak at about 68.0 eV was detected in BC-3 as rectangle marked.
The high resolution in Fig. 2b with two fitted peaks at 68.3 eV and 69.3
eV are assigned to Br 3d5/2 and Br 3d3/2, respectively [26]. By contrast,
not any signal is monitored in bare BOC at the same position. In Fig. 2c,
the peaks located at 159.2 eV and 164.5 eV in BC-3 are ascribed to Bi
4f7/2 and Bi 4f5/2 of Bi(III). But they are shifted to a higher position by
0.2 eV compared with that of BOC. It indicates the alteration of charge
distribution of Bi atom due to the interface effect of BOC and BiOBr [32].
The asymmetric O 1s peak in Fig. 2d is resolved into lattice oxygen of
Bi–O and C–O at 530.1 eV and 531.1 eV in BC-3, respectively. For the C
1s spectrum in Fig. 2e, the peak at 288.9 eV comes from the CO23 ion in
BC-3 besides the adventitious signal at 284.8 eV from the XPS instru­
ment. A higher shift of the binding energy also occurs in the O 1s and C
1s spectra of BC-3, further confirming the strong interaction of BiOBr
Fig. 4. (a) DRS spectra of BOC, BiOBr and BC-3 samples with band energy in and BOC. The EDS profile in Fig. 2f also reveals the existence of Br
inset, (b) PL spectra (λex ¼ 280 nm) of BOC and BC hybrids. element in BC-3 composite.

2550 UV–vis spectrophotometer. The same procedure was used to 3.2. Morphology and microstructure
appraise the photocatalytic degradation of methylene blue (MB), methyl
orange (MO), crystal violet (CV) and phenol. SEM and TEM images were recorded to explore the microscopic
structure of BOC-based samples. As indicated in Fig. 3a, the bare BOC is
2.4. Photocurrent and EIS measurement of cluster-shaped structure aggregated by irregular slices with 100–300
nm in side edge and 25–30 nm in thickness. The loose assembly of the
The measurement of transient photocurrent and electrochemical nanosheets should be beneficial for the light scattering and the transport
impedance spectroscopy (EIS) was operated with a Versa START4-200 of reactive species [33]. All the BC composites inherit the cluster
electrochemical work station. The photocatalyst powder of 50 mg was morphology of BOC substrate (Fig. 3b and Fig. S1) and the surface Br
dispersed homogeneously in a mixture of 4 mL DMF and 50 μl Nafion. content is gradually increased from BC-1 to BC-4 as revealed by EDS
Then 0.5 mL of the suspension was drop-casted onto an ITO glass and spectra (Fig. S1). However, the nanosheet surfaces of BC samples
vacuum-dried at 60 � C to get the working electrode. An Ag/AgCl elec­ become somewhat rough compared with that of BOC, indicating the
trode and Pt wire were used as the reference and counter electrodes, in-situ transformation of trace BiOBr on BOC surface by ion etching.
respectively. Na2SO4 aqueous solution of 0.5 M was used as electrolyte Fig. 3c gives the TEM image of a BC-3 cluster with diameter of 1.5 μm, in
and the simulated solar illumination was provide by a 300 W Xe lamp. which it is seen that the structure is assembled by nanosheets intersected
with each other and agrees well with the SEM result. However, the
enlarged observation as circle marked shows that some tiny particles of
3.0–4.0 nm appear on the BOC nanoplate surface. Due to the decorated
BiOBr particles, the BET surface area of BC-3 is enhanced with an

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J.-j. Wang et al. Solid State Sciences 105 (2020) 106288

Fig. 5. (a) Photocatalytic degradation of RhB over BOC-based samples and (b) corresponding dynamic plots, (c, d) temporal evolution of RhB absorption spectra over
BC-3 and BOC, respectively.

obviously improved adsorption quantity (Fig. S2). The HRTEM image of 340 to 420 nm, which result from the backward transition of photoin­
BC-3 nanosheet in Fig. 3d shows a clear interface [34] of BOC substrate duced electrons from conductance band (CB) to valence band (VB).
and BiOBr nanoparticle, and their corresponding lattice fringes with However, the PL intensities of the BC composites are all lowered than
d-spacing of 0.273 nm and 0.277 nm consist well with the facets of BOC that of bare BOC. It indicates that the carrier recombination in BC hy­
{110} and BiOBr {110}, respectively. The selected area electron brids is effectively restrained owing to the formation of a built-in electric
diffraction (SAED) in inset taken from the BOC substrate with field between BOC and BiOBr semiconductors. The emission peak of
well-defined dot pattern is indexed as a BOC single crystal recorded BC-3 with Br-0.094 wt% is quenched to the minimum. It indicates that
along the [001] zone axis. So, the exposed facet of BOC belongs to {001} proper amount of BiOBr is needed to establish a balance in the separa­
plane, as previously confirmed to be the active facet [35]. The EDX tion and recombination of carriers [38].
mapping in Fig. 3e–g shows that Br element distributed uniformly on the
surface of BOC. The weak Br signal results from the trace amount of 3.4. Photocatalytic properties
BiOBr and corresponds well with the XRD, IC and EDS results.
To probe the activity of BOC and BC hybrids, photocatalytic degra­
3.3. Optical property dation of organic pollutants was carried out under simulated solar
illumination. As depicted in Fig. 5a, the photolysis of RhB solution
The optical property of the samples were investigated by DRS and PL without photocatalyst is very weak and can be neglected. Under the
techniques. Fig. 4a reveals the UV–vis absorption spectra of BOC, BiOBr catalysis of pristine BOC and BiOBr, about 31.8% and 74.9% of RhB is
and BC-3 hybrid. The bare BOC presents absorption in UV region with a decolorized after 20 min irradiation, respectively. In comparison, all the
threshold wavelength located at 366 nm. While BiOBr has a broad BC hybrids perform superior adsorption ability and enhanced photo­
photo-response in the region from ultraviolet to visible light of 450 nm. catalytic activity than bare BOC, in which BC-3 presents the best pho­
The BC-3 with trace BiOBr has a similar absorption shape with BOC but toactivity with a degradation efficiency reached up to 99.5% under
exhibits a slight red-shift from 366 nm to 382 nm. Based on Kubelka- identical conditions. The dynamics plots in Fig. 5b reveals the corre­
Munk equation, the band gap energy Eg can be estimated from the sponding rate constant (k) in an order of BC-3 > BC-4 > BC-2 > BiOBr >
curve of (αhν)1/2 vs. hν for an indirect semiconductor, where hν is the BC-1 > BOC. In specific, the k value of 0.2562 min 1 for BC-3 is boosted
photon energy and α is the absorption coefficient [36]. The inset in by ca. 14.8 and 4.03 folds than that of bare BOC (0.0173 min 1) and
Fig. 4a shows that the Eg of BOC, BiOBr and BC-3 is 3.39, 2.75 and 3.25 BiOBr (0.06357 min 1), respectively. Excess BiOBr may shade the active
eV, respectively. The narrowed band gap of BC-3 indicates the slightly sites of BOC and become the recombination centers of photoinduced
widened light harvesting of BOC with the decoration of BiOBr. charges. So a balanced amount of BiOBr is crucial to optimize the pho­
The charge transfer behavior of a photocatalyst is widely researched toactivity of BOC.
by PL technique. Usually, a lower PL intensity indicates a decreased Fig. 5c and d shows the time evolution of RhB absorption spectra
recombination of photogenerated e /hþ pairs [37]. The PL spectra of under the photocatatlysis of BOC and BC-3, respectively. As depicted in
BOC and BC hybrids excited at 280 nm were given in Fig. 4b. The spectra Fig. 5c, the RhB absorption peak decays rapidly over BC-3 with
shapes of the samples are almost the same with a broad emission from continued exposure time and a complete discoloration is achieved after

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3.5. Photocatalytic active species

Scavenger experiment was performed to explore the reactive species

in the oxidation process of RhB over BC-3. Ammonium oxalate (AO),
isopropanol (IPA) and benzoquinone (BQ) were used as sacrificial agents
for hþ, ⋅OH and O2 ⋅, respectively. As shown in Fig. 7a, the removal rate
of RhB reduces greatly in the presence of 0.1 mM AO and BQ, in which
the degradation efficiency decays from 99.5% to 23.3% and 46.5% after
20 min irradiation, respectively. However, only a slight inhibition of ca.
4.9% is observed when IPA is added with other conditions unchaged. It
indicate that hþ and O2 ⋅ play major roles to the oxidation of RhB and the
⋅OH just makes a minor contribution. The radical effect was further
studied by ESR techniques with a spin-trapping reagent of 5,5-dimethyl-
1-pyrroline-N-oxide (DMPO). As indicated in Fig. 7b and c, not any O2 ⋅
or ⋅OH signal can be observed in the dark. After illumination for 1.0 min,
the characteristic DMPO-O-2⋅ multiple peaks and DMPO-⋅OH quartet
peaks [42] have been clearly detected. For DMPO-O-2⋅, the signal in­
tensity slightly increases with prolonged irradiation to 5.0 min. While in
the case of DMPO-⋅OH, the peaks are relatively low and even become
weaker with time extension. It shows that light irradiation is crucial to
the generation of radicals and O2 ⋅ is more important than ⋅OH, in good
consistence with the scavenger results.

3.6. Photoelectrochemical analyses

The photocatalytic activity of a catalyst is greatly influenced by the

transfer behavior of photoinduced carriers. Transient photocurrent and
ESI techniques can furnish compelling proof for the carrier migration in
a photocatalyst [43]. Usually, a small semicircle in the ESI Nyquist plot
and a high photocurrent are indicative of a fast interfacial
charge-transfer and electrode reaction [44]. The Nyquist plots of BOC
and BC-3 hybrid before and after illumination were given in Fig. 8a. The
arc radius of the two samples is both reduced under the exposure of
light, indicating the effective production of photoinduced charges. It is
noticeable that BC-3 presents an obviously smaller semicircle than bare
BOC whether in the dark or under irradiation. It reveals that the
photoinduced carrier is effectively separated and a lower charge
migration resistance is established at the electrode interface of BC-3
Fig. 6. (a) Circulation runs of BC-3, (b) visible light photocatalytic degradation [45]. The photocurrent response curves of BOC and BC hybrids were
of phenol over BOC and BC-3. given in Fig. 8b. The samples are all steady and reproducible during
several on-off intermittent irradiation cycles. The photocurrent of BOC is
28 min irradiation. Meanwhile, the maximum absorption peak gradually relatively low and indicative of the fast recombination of photo­
blue-shifts from 554 nm to 498 nm during the degradation. It indicates generated e /hþ pairs. All the BC hybrids show greatly boosted photo­
that the de-ethylation by photosensitization is also included in the RhB current densities in a sequence of BC-3 > BC-4 > BC-2 > BC-1, in good
degradation [39]. The molar absorptivity of the complete de-ethylation agreement with their photoactivity. In particular, the photocurrent
is reported to be 70.0% of the original absorption of RhB [40]. Herein, density of BC-3 is dramatically promoted by ca. 7.0 times than that of
the dramatic absorption decay to 11.5% at 498 nm over BC-3 indicates BOC. The photoelectrochemical results confirm the effective formation
that the photosensitization plays a minor role in the RhB degradation. It of BiOBr/BOC heterojunction, which accelerates the separation and
is the photocatalysis that dominates the RhB degradation. In contrast, migration of carriers and elevates the photocatalytic activity.
the RhB degradation over BOC (Fig. 5d) is much more slower, in which
the entire decolorization is finished after 80 min irradiation. 3.7. Interface charge migration mechanism
The lifetime of a photocatalyst is an important factor for practical
application. Recycle photoactivity experiment of BC-3 was conducted The migration direction of photoinduced carrier in a heterojunction
with results in Fig. 6a. A satisfied degradation efficiency is kept in the is determined by the band edge positions of semiconductors, which can
circulation runs with no obvious catalyst deactivation. The small decay be estimated based on the equation EVB ¼ X - Ec þ 0.5Eg Refs. [46].
of 12.4% after 5 cycles is due to the residually adsorbed RhB, which Wherein, EVB is the edge potential of valence band, X is the Mulliken’s
would occupy some active sites of BC-3 [41]. Not any distinct change is electronegativity of a photocatalyst, and Ec is the energy of free electrons
observed in the SEM and Br 3 d XPS in BC-3 recovered after the 5th cycle on the hydrogen scale (4.50 eV). The X values of BiOBr and BOC are
(Fig. S3). The photocatalytic experiment was further applied to phenol, a 6.17 eV and 6.33 eV, and their Eg are estimated to be 3.39 and 3.25 from
much more stubborn pollutant. As shown in Fig. 6b, it can be photo­ DRS spectra, respectively. By calculation, the EVB and ECB of BiOBr are
degraded by BOC-based catalysts in a longer exposure time and the rate 3.05 and 0.30 eV, and the corresponding vales of BOC are 3.53 and 0.14
constant k of BC-3 is improved by 1.9 folds than BOC. The degradation to eV, respectively. Obviously, the VB level of BiOBr is higher and the CB
dyes of MB, MO and CV with superior efficiency (Fig. S4) also confirms level is lower than that of BOC. As schematically shown in Fig. 9, the
the advantage of the as-designed BiOBr/BOC heterojunction. nested band structure seems to be unfavorable for the charge transfer. In
fact, BiOBr and BOC are semiconductors of p-type and n-type, respec­
tively. A p-n heterojunction would be generated when they are in contact

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Fig. 7. (a) Reactive species trapping experiments; ESR spectra of radical adducts trapped by DMPO over BC-3 in (b) methanol (DMPO-O-2⋅) and (c) aqueous (DMPO-
⋅OH) dispersions, respectively.

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with each other. As sketched in the right half of Fig. 9, the electrons of
n-type BOC would diffuse to p-type BiOBr and result in an accumulation
of negative charges in BiOBr section. Meanwhile, the holes migrate from
p-type BiOBr to n-type BOC, leaving a positive area in BOC near the
heterojunction. Resultantly, the energy band of BOC shifts downward
and that of BiOBr shifts upward until an equilibrium state of their Fermi
levels (Ef) is achieved [47]. The lowered VB level of BOC in the heter­
ojunction agrees well with the more anodic XPS-VB value of BC-3 than
that of bare BOC (Fig. S5). Thus, a built-in electric field and an II-type
band matching are established at the interface of BiOBr and BOC.
Under the irradiation of simulated sunlight, electrons are photoexcited
to the CB and holes are left on the VB in the two semiconductors. Forced
by band potential differences, the CB electrons of BiOBr inject to the CB
of BOC and meanwhile the VB holes of BOC migrate to that of BiOBr. In
such a way, the photoinduced e /hþ pairs are effectively separated, as
has been evidenced by previous PL and photoelectrochemical results.
The holes would directly serve as oxidizing agent for organic contami­
nants as the most important active species. As for the electrons, the CB
electrons in BOC cannot be captured by O2 to generate O2 ⋅ radicals due
to its more positive CB level than the redox potential of O2/O2 ⋅ ( 0.046
V vs. NHE) [48]. While on the side of BiOBr, the energy band shifts
upward and when the CB level shifts to a potential higher than 0.046
V, the O2 ⋅ radical would be produced by some electrons before there are
transferred to the CB level of BOC. The up-shifted VB level of BiOBr may
comparative to the electrode potential of ⋅OH/H2O (2.38 eV vs NHE). So
it is difficult for ⋅OH to be generated, which only act as a minor role in
the photocatalysis. Under the p-n heterojunction effect, a boosted pho­
toactivity of BiOBr/BOC is obviously achieved.

4. Conclusions

In summary, an efficient BiOBr/BOC heterostructure was fabricated

through a simple precipitation transformation strategy at ambient
temperature. The decoration of trace p-type BiOBr dramatically boosts
the photocatalytic activity of n-type BOC. Specially, the BC hetero­
juntion of Br-0.094 wt% possesses the optimal photoactivity, in which
the rate constant k towards RhB degradation is enhanced by 14.8 times
compared with bare BOC. The charge separation and transfer in BiOBr/
Fig. 8. (a) EIS Nyquist plots of BOC and BC-3, (b) photocurrent response BOC heterojunctions is greatly improved as evidenced by photocurrent,
spectra of BOC and BC composites. ESI and PL results. The reason is ascribed to the established built-in
electrical field and the resulted band matching between BiOBr and
BOC semiconductors. Based on the p-n junction effect and the detected

Fig. 9. Schematic diagram of the separation and migration of photoinduced charges at the BiOBr/BOC interface under simulated solar irradiation.

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oxidative species, a mechanism of charge migration path in the interface [15] N. Guo, Y. Cao, Y. Rong, D.Z. Jia, Green synthesis of BiOBr modified Bi2O2CO3
nanocomposites with enhanced visible-responsive photocatalytic properties, RSC
of BiOBr and BOC was put forward.
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