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Engineering BiOX (X ¼ Cl, Br, I) nanostructures for

highly efficient photocatalytic applications
Cite this: Nanoscale, 2014, 6, 2009
Hefeng Cheng,a Baibiao Huang*a and Ying Daib

Received 17th October 2013
Accepted 18th November 2013
DOI: 10.1039/c3nr05529a
www.rsc.org/nanoscale
Heterogeneous photocatalysis that employs photo-excited semiconductor materials to reduce water and
oxidize toxic pollutants upon solar light irradiation holds great prospects for renewable energy substitutes
and environmental protection. To utilize solar light effectively, the quest for highly active photocatalysts
working under visible light has always been the research focus. Layered BiOX (X ¼ Cl, Br, I) are a kind of
newly exploited efficient photocatalysts, and their light response can be tuned from UV to visible light
range. The properties of semiconductors are dependent on their morphologies and compositions as well
as structures, and this also offers the guidelines for design of highly-efficient photocatalysts. In this
review, recent advances and emerging strategies in tailoring BiOX (X ¼ Cl, Br, I) nanostructures to boost
their photocatalytic properties are surveyed.

purication and harmful pollutant removal. Hence, consider-

1. Introduction
With the huge consumption of traditional fossil fuels in the
past several centuries, including coal, crude oil and natural gas,
human beings are now confronting a great energy crisis and
environmental pollution issues. Semiconductor photocatalysis,
which could utilize the abundant solar energy for water splitting
into H2 gas,1–3 harmful pollutant decomposition,4,5 selective
organic transformations6,7 and CO2 conversion to energy-
bearing carbon fuel sources,8–10 has been regarded as an effi-
cient, green and promising solution to energy replacement and
environmental decontamination. The conventional TiO2 pho-
tocatalyst,11–16 however, is conned by its wide band gap (e.g.,
3.0 eV for rutile and 3.2 eV for anatase) and responds only to UV
light that accounts for less than 5% of sunlight energy. In order
to take full advantage of the abundant solar energy or indoor
illumination, it is of crucial signicance to develop visible-light-
driven photocatalysts with high efficiency.
In efforts to exploit novel photocatalyst systems working
under visible light, it has been revealed that orbitals of some
p-block metals with a d10 conguration,3,17–19 such as Ag 4d in
Ag(I), Sn 5s in Sn(II) and Bi 6s in Bi(III), could hybridize O 2p
levels to form a new preferable hybridized valence band (VB),
thus narrowing the band gap to harvest visible light. In terms of
low toxicity and earth abundance, bismuth-based materials are
more appropriate candidates; on the other hand, bismuth-
based semiconductors (e.g., Bi2O3,20,21 CaBi2O4,22 Bi2WO6,23–26
BiVO4,27–31 Bi4Ti3O12,32,33 Bi2O2CO334,35 and BiOIO336) have
shown efficient photocatalytic performances in waste water
able attention has been drawn to the bismuth-based semi-
conductors, which could be endowed with strong visible light
absorption and excellent photocatalytic activity.
Bismuth oxyhalides BiOX (X ¼ Cl, Br, I), as another category
of Bi-based semiconductors, are of immense importance for
their outstanding optical and electrical properties and have
exhibited promising applications in pharmaceuticals,37
pigments38 and catalysts,39 as well as gas sensors.40 All BiOX (X ¼
Cl, Br, I) compounds are crystallized in a tetragonal matlockite
structure. Taking BiOCl for example, as illustrated in Fig. 1,
BiOX (X ¼ Cl, Br, I) are characterized by the layered structure
that are composed of [Bi2O2] slabs interleaved with double
halogen atom slabs along the [001] direction. Inspiringly, Zhang
et al.41 have recently reported the exceptional photocatalytic
property of BiOCl, which exhibited superior activity to
commercial P25 towards methyl orange (MO) dye degradation
under UV irradiation. It is noted that with increasing atomic
numbers, the band gaps of BiOX (X ¼ Cl, Br, I) become narrower

a
State Key Lab of Crystal Materials, Shandong University, Jinan 250100, China.
E-mail: bbhuang@sdu.edu.cn; Fax: +86-531-88365969; Tel: +86-531-88364449 Fig. 1 The schematic diagram of (a) unit cell and (b) crystal structure of
b
School of Physics, Shandong University, Jinan 250100, China BiOCl.

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for BiOCl (3.2 eV), BiOBr (2.7 eV) and BiOI (1.7 eV), which
could allow one to maximize their photocatalytic activities in a
large range. Since this pioneering work, exponential interests
have been focused on the robust syntheses of BiOX (X ¼ Cl, Br, I)
nano/micro-structures to boost their photocatalytic activi-
ties.42–82 It has become of great importance and necessity to
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summarize the design, preparation, and corresponding photo-
catalytic applications of BiOX-related nanomaterials in the last
few years. Nevertheless, reviews outlining the utilization of such
new-type ternary semiconductor nanostructures for heteroge-
neous photocatalysis have not been available. In this review, we
aim to ll this gap and cover the recent advances in BiOX (X ¼
Cl, Br, I) photocatalysts to give an insight into the structure–
property correlation. In addition, we will emphasize the
engineering of BiOX (X ¼ Cl, Br, I) nanomaterials for efficient
photocatalytic applications, which can be classied into
microstructure modulation, heterologous hybridization and
structural design. In this context, some BiOX (X ¼ Cl, Br, I)
nanomaterials83–92 that are absent from photocatalytic applica-
tions will not be discussed thereinaer.
2. Microstructure modulation of BiOX
photocatalysts
Owing to the strong correlation between the physical/chemical
properties and the microstructure (i.e., shape, size, surface area
and dimensionality) of the materials, rational synthesis of novel
nano- or micro-architecture has always been of great impor-
tance for both scientic research and industrial applica-
tions.93–95 With respect to their bulk counterparts,
nanomaterials that are dened as materials with lengths in the
range of 1–100 nm in at least one direction, usually possess
exceptional optical and electrical properties derived from their
quantized sizes.93 Furthermore, nanomaterials are endowed
with a higher surface-to-volume ratio and more active sites,
which will facilitate the separation of the photo-generated
carriers and then improve the photocatalytic efficiency of BiOX
(X ¼ Cl, Br, I) semiconductors. Recently, a variety of BiOX (X ¼
Cl, Br, I) nano-/microstructures, including one dimensional
(1D) nanorods/wires,42–44 two dimensional (2D) nanoplates/
sheets,41,45–52 and three dimensional (3D) hierarchical architec-
tures53–82 as well as supported thin lms96–102 have been
synthesized to maximize their photocatalytic applications. The
relevant parts will be discussed in detail in the following
sections (Table 1).
2.1 1D templated nano-bers/wires
1D nanostructures, namely, are classied to the materials with
thickness and width in the nanoscale range, while the length
can be several micrometers or longer. The prolonged length
scale could enable the 1D nanomaterials to contact the
macroscopic world for various measurements.103,104 In addition,
the high aspect ratio of 1D nanostructured semiconductors also
facilitates the fast separation of the photoinduced electrons and
holes, which is favorable for highly efficient photocatalytic
reactions.
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Due to their highly anisotropic layered structures, BiOX (X ¼
Cl, Br and I) tend to grow into nanoplates/sheets with 2D
features. As a result, the realization of 1D bismuth oxyhalide
nanostructures is usually resorted to the hard templates, which
can be easily removed by subsequent thermal or chemical
treatments.42–44 For example, Liu et al.42 adopted the electro-
spinning method to synthesize BiOCl nanobers, as shown in
Fig. 2. Aer thermal treatments of the polyacrylonitrile (PAN)
template at 500  C for 10 h, BiOCl nanobers with diameters
ranging from 80 to 140 nm were obtained. Interestingly, the as-
prepared BiOCl nanobers showed high activity towards
Rhodamine B (RhB) degradation under UV irradiation, which
was about 3 times faster than that of Bi2O3 nanobers obtained
in the same way. In addition to PAN, some other templates
involving activated carbon bers (ACFs)43 and anodic
aluminium oxide (AAO)44 have also been employed to prepare
BiOCl nanobers/nanowire arrays, which displayed efficient
photocatalytic performance in the degradation of organic dyes.
2.2 2D intrinsic nanostructures
In the past few years, 2D nanomaterials, such as graphene,
transition metal dichalcogenides and layered double hydrox-
ides (LDHs), have received great attention for their exotic
physical/chemical features and promising applications in a
variety of elds.105–108 Intrinsically, such 2D nanostructures arise
from their lamellar structures, which are built by the inter-
laminated weak van der Waals bonds or electrostatic forces.
Similarly, the layered structure renders BiOX (X ¼ Cl, Br, I)
prone to the intrinsic 2D nanostructures, involving nanoplates,
nanosheets and nanoakes. The formed intra-electric eld
between [Bi2O2] layers and halogen atom layers could accelerate
the transfer of the photo-induced carriers and enhance the
photocatalytic activity of BiOX (X ¼ Cl, Br, I).41
To date, numerous synthetic methodologies have been
exploited for the preparation of 2D BiOX nanomaterials, such as
hydrolysis,41,45–48 hydrothermal/solvothermal synthesis,49–51 and
thermal annealing.52 For instance, by selective addition of the
mineralizing agent NaOH, Zhang's group49 has recently
prepared 2D BiOCl nanosheets with predominantly exposed
{001} and {010} facets, respectively, by hydrothermal synthesis.
Interestingly, BiOCl nanosheets with exposed {001} facets dis-
played higher UV-induced photocatalytic degradation of MO
dye, whilst the counterpart with exposed {010} facets exhibited
higher degradation activity under visible light. As shown in
Fig. 3, on one hand, the generated internal electric eld along
the [001] direction is more favorable for direct semiconductor
photoexcitation under UV irradiation, which was also
conrmed by the higher photocurrent of {001} facets than that
of {010} facets from the transient photocurrent responses. On
the other hand, compared to {001} facets, the larger surface area
and open channel feature of {010} facets facilitate the adsorp-
tion of dye molecules, thus leading to its better indirect dye
photosensitization performance under visible light irradiation.
Such a facet-dependent photocatalytic property in BiOX (X ¼ Cl,
Br, I) was also studied through density functional theory (DFT)
computations.109 The halogen X-terminated {001} facets possess
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Table 1 Recent studies on BiOX (X ¼ Cl, Br, I) nanostructures and their corresponding photocatalytic applications

Samples Synthetic procedures Photocatalytic applications Ref.

1D template nanostructures
BiOCl nanobers Electro-spinning Completely RhB degraded within 60 min (UV) 42
BiOCl bers Solvothermal synthesis (ethanol) 75% MO mineralization in 110 min (UV) 43
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BiOCl nanowire arrays Sol–gel Almost 100% RhB degradation within 130 min (UV) 44

2D intrinsic nanostructures
BiOCl plates Hydrolysis Completely MO degradation within 10 min (UV) 41
BiOCl nanosheets Hydrolysis About 2 times higher RhB photodegradation rate 45
than that on P25 (UV)
BiOBr lamellas Hydrolysis Completely RhB degraded within 30 min (Vis) 46
BiOX (X ¼ Cl, Br, I) nanosheets Hydrolysis 95.9% sodium pentachlorophenate (Na-PCP) degradation 47
on BiOI within 1 h following BiOI > BiOBr > BiOCl (Xe-lamp)
BiOCl nanosheets Hydrothermal synthesis About 99% MO degradation within 45 min (UV) 49
BiOCl nanoplates Mannitol-assisted Completely RhB disappearance within 8 min (Vis) 50
hydrothermal synthesis
BiOBr lamellar Hydrothermal synthesis 96% MO degraded within 120 min (Vis) 51
BiOI nanosheets Thermal annealing 7 times higher photoactivity than that 52
on irregular BiOI (Vis)

3D assembled hierarchical architectures

BiOX (X ¼ Cl, Br, I)
nanoplate microspheres
BiOX (X ¼ Cl, Br, I)
hierarchical architectures
BiOCl porous nanospheres
BiOCl nano-owers
BiOCl hierarchical architectures
BiOCl hierarchical self-assemblies
BiOCl micro-owers
BiOBr microspheres
BiOBr nanoplate microspheres
BiOBr microspheres
BiOBr hollow microspheres
BiOBr micro-owers
BiOBr porous nanospheres
BiOBr microspheres
BiOBr microspheres
BiOBr 3D microspheres
BiOBr microspheres
BiOBr mesoporous microspheres
BiOI hierarchical structures
BiOI hollow microspheres
BiOI micro-owers
BiOCl nano-owers
BiOCl sub-microcrystals
BiOI micro-owers
BiOI microspheres
BiOCl hierarchical owers
BiOBr fullerene-like eggshells
BiOCl 3D desert roses
Solvothermal synthesis (EG)
Solvothermal synthesis
(2-methoxyethanol, EG)
Solvothermal synthesis (EG)
Solvothermal synthesis (pyridine)
Solvothermal synthesis (EG)
Hydrothermal synthesis
Hydrothermal synthesis
(glycerol + H2O)
Solvothermal synthesis (EG)
Solvothermal synthesis (EG)
Solvothermal synthesis (EG)
Solvothermal synthesis
(2-methoxythanol)
Solvothermal synthesis (EG)
Solvothermal synthesis (EG)
Microwave-assisted
solvothermal synthesis (DEG)
Solvothermal synthesis (TEG)
Solvothermal synthesis (ethanol)
Solvothermal synthesis
(isopropanol + EG)
Solvothermal synthesis (ethanol)
Hydrothermal synthesis
Solvothermal synthesis (EG)
Solvothermal synthesis (EG)
Hydrolysis
Hydrolysis
Direct precipitation
Direct precipitation
Sonochemical route
Ultrasound reaction
and heating synthesis
Reuxing method
80% MO degraded on BiOI within 3 h with the 53
order BiOI > BiOBr > BiOCl (Vis)
Completely MO degradation on BiOI within 60 min 54
with the order BiOI > BiOBr > BiOCl (Vis)
Almost 100% RhB degraded within 2 h (Vis) 55
Completely MO degradation within 10 min (UV) 56
Completely degrade RhB within 60 min (UV) 57
90.2% RhB degraded within 50 min (UV) 58
99.3% RhB degraded within 15 min (Vis) 59
Higher MO degradation than that on 60
BiOBr bulk plates (Vis)
Nearly 30% NO removal within 10 min (Vis) 61
100% tetrabromobisphenol A decomposed 62
within 15 min under simulated sunlight
100% RhB degraded in 15 min and 90% Cr(VI) 63
reduced in 20 min (Vis)
92.5% MB degraded for 4.5 h (Vis) 64
RhB completely degraded within 105 min (Vis) 65
99% phenol decomposed within 80 min (UV) 66
90% Micrococcus lylae inactivated aer 67
6 h under uorescent light
Toluene conversion rate 2-fold larger than 68
that on P25 under simulated sunlight
95% RhB degraded within 40 min (Vis) 69
Nearly 100% bisphenol A degradation within 70
90 min under simulated sunlight
MO completely degraded within 50 min (Vis) 71
92% MO degraded within 3 h (Vis) 72
80% RhB degraded within 4 h (Vis) 73
Completely RhB degradation within 50 min (Vis) 74
99.5% RhB decomposed within 75 min (UV) 75
100% RhB degraded within 2 h (Vis) 76
94% tetracycline hydrochloride 77
decomposed within 2 h (Vis)
90% MO degraded aer 1 h under 78
simulated sunlight
Over 95% RhB degraded within 25 min (Vis) 79
Completely RhB degraded within 20 min (Vis) 80

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Table 1 (Contd. )

Samples Synthetic procedures Photocatalytic applications Ref.

BiOI microspheres Chemical bath 97% phenol decomposed within 4 h (Vis) 81

BiOCl 3D owers Solution oxidation process 100% RhB degraded within 80 min (Vis) 82
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Supported thin lms

BiOCl nanosheet arrays Solvothermal synthesis Comparable MO degradation rate and better 96
(methanol + EG) durability than that on P25 lm (UV)
BiOCl thin lm Electrochemical route Completely MO degradation within 97
150 min at 2.0 V voltage bias (UV)
BiOCl nanoakes lm Hydrolysis Durable superhydrophobicity when 98
modied with FDTS (UV)
BiOCl lms Hydrolysis 100% RhB degradation within 2 h (UV) 99
BiOI thin lms Chemical vapor transport 90% RhB degradation within 2 h (Xe-lamp) 100
BiOI ake array Successive ionic layer Maximum IPCE of about 4% under simulated sunlight 101
adsorption and reaction
BiOI nanoplatelet lms Spray pyrolysis Maximum IPCE of over 20% (Vis) 102

the band gap. This nding reveals the insight into the facet-
determined photocatalysis of BiOX (X ¼ Cl, Br, I), and indirectly
explains the superior photocatalytic performance of BiOX (X ¼
Cl, Br, I) nanosheets with higher percentage of {001} facets than
those with lower ones.45,46,52

2.3 3D assembled hierarchical architectures

Fig. 2 SEM images of the prepared (A) PAN/BiCl3 nanofibers and (B)
BiOCl nanofibers.42 Reprinted with permission from Elsevier.
Fig. 3 (a) Crystal structure of BiOCl. (b) Model showing the direction
of the internal electric field in each of the BiOCl nanosheets. (c)
Photocurrent responses of the BiOCl nanosheets in 0.5 M Na2SO4
aqueous solutions under UV-vis irradiation.49 Reprinted with permis-
sion from American Chemical Society.
thermodynamic stability and could separate photo-generated
electron–hole pairs efficiently, whereas BiX-terminated {110}
and other facets with surface O vacancies are detrimental to the
carrier separation due to the formation of deep defect levels in
As an essential part of nanotechnology, self-assembly of low-
dimensional (e.g., 1D nanorods, 2D nanosheets) building
blocks into their higher-order (3D) multifunctional super-
structures has been paid more and more attention and plays a
great role in material synthesis and device engineering.110–114 In
comparison with 1D and 2D nanostructures, 3D hierarchical
nano-/microstructures are more attractive for solar energy
storage and conversion, which integrate the features of the
nanoscale building units and their assembled architec-
tures.112–114 Furthermore, 3D architectures could endow the
BiOX (X ¼ Cl, Br, I) semiconductors with improved light har-
vesting, shortened diffusion pathways, faster interfacial charge
separation and more reactive sites, thus enhancing their pho-
tocatalytic efficiencies.
Among the methodological syntheses of the 3D BiOX (X ¼ Cl,
Br, I) hierarchical assemblies, hydro-/solvothermal routes are
denitely the most robust,53–72 which are usually carried out at
critical conditions of water or other organic solvents. In 2008,
Zhang et al.53 adopted a generalized solvothermal process in the
presence of ethylene glycol (EG) to prepare BiOX (X ¼ Cl, Br, I)
hierarchical microspheres, which are composed of 2D nano-
plates by self-assembly. The band gaps of the resulting BiOX
(X ¼ Cl, Br, I) samples are calculated to be 3.22, 2.64, and
1.77 eV for BiOCl, BiOBr, and BiOI, respectively. Evaluated by
MO dye solution degradation under visible light irradiation, the
BiOI sample exhibited the best photocatalytic performance with
the order of BiOI > BiOBr > BiOCl. Almost at the same time,
Tang et al.60 also prepared 3D microspherical BiOBr architec-
tures assembled by nanosheets through EG-assisted sol-
vothermal synthesis. With the band gap of 2.54 eV, the BiOBr

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architectures showed higher photocatalytic activity for MO
decomposition under visible light irradiation than the BiOBr
bulk plates.
In the microstructure modulation of BiOX (X ¼ Cl, Br, I)
nano-/microstructures, the realization of hierarchical architec-
tures with hollow voids are more fascinating when derived from
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their better penetrability and higher light utilization. Recently,
our group63 has developed a mini-emulsion mediated sol-
vothermal route to synthesize uniform BiOBr hollow micro-
spheres in the presence of 2-methoxyethanol solvent. With
diameters in the range of 1–2 mm and shell thickness of about
100 nm, the BiOBr hollow microspheres are built by numerous
interlaced 2D nanosheets. As illustrated in Fig. 4, the 1-hexa-
decyl-3-methylimidazolium bromide ionic liquid ([C16Mim]Br
IL) not only performs as a Br source, but also gives rise to
colloidal mini-emulsions, conrmed by the observed Tyndall
effect of the precursor suspension. The reaction takes place at
its phase interface of the mini-emulsion rather than in the
emulsion itself, thus maintaining the dimensions of the
micelles. Under visible light irradiation, such BiOBr hollow
microspheres displayed superior photocatalytic activity in
degradation of RhB dye and reduction of CrVI ions to the
samples with micro-ower shape. Using 1-butyl-3-methyl-
imidazoliumiodine ([Bmim]I) IL as the reactive templates and I
source, Xia and co-workers72 prepared BiOI hollow micro-
spheres by the EG-assisted solvothermal method. Under visible
light irradiation, such 3D BiOI hollow microspheres exhibited
higher photocatalytic activity towards MO degradation than
that of 2D BiOI nanoplates. Besides the halide ion-containing
ILs,54,55,63,65,67,72 surfactants such as poly(vinylpyrrolidone)
(PVP)58 and hexadecyltrimethylammonium bromide
(CTAB)61,62,64,66,68,69 have also been employed to tailor the self-
assembly process of the BiOX (X ¼ Cl, Br, I) hierarchical
architectures, and in particular CTAB could act as reactable
template to provide Br ions for BiOBr.
Fig. 4 The schematic formation process of the BiOBr hollow micro-
spheres by the mini-emulsion mediated solvothermal route.63
Reprinted with permission from Wiley-VCH.
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In addition to the hydro-/solvothermal syntheses, other
synthetic protocols including hydrolysis,74,75 direct precipita-
tion,76,77 sonochemical route,78,79 reuxing method,80 chemical
bath81 and solution oxidation process,82 are also employed to
obtain the ordered superstructures of BiOX (X ¼ Cl, Br, I)
semiconductors. For example, Xiong and co-workers82 reported
a rapid in situ oxidation process to fabricate 3D ower-like
BiOCl hierarchical nanostructures by reacting metallic Bi
nanospheres and FeCl3 aqueous solution at room temperature.
As presented in Fig. 5, in the presence of Cl ions, the redox
potential of Bi species could be reduced from +0.308 V (Bi3+/Bi
vs. SHE) to +0.16 V (BiOCl/Bi). Therefore, the high redox
potential of Fe3+ (E(Fe3+/Fe2+) ¼ +0.771 V) could oxidize the
surface of Bi nanospheres into the nal 3D BiOCl hierarchical
nanostructures. Compared to the commercial BiOCl sample,
such obtained ower-like BiOCl nanostructures displayed much
better RhB photodegradation activity and higher photoelectric
conversion performance.
2.4 Supported thin lms
As one important category of the 2D nanostructures, BiOX thin
lms on solid substrates have recently attracted much interest
owing to their easy reclamation and long-term use.96–100 Mu
et al.96 prepared vertically aligned BiOCl nanosheet arrays on the
uorine-doped tin oxide (FTO) substrate by a solvothermal
method. They found that BiOCl nanosheet arrays showed a
comparable MO degradation rate and superior durability to P25
lm under UV irradiation. Moreover, the construction of sup-
ported BiOX lms opens up the possibility to investigate their
surface wettability. Recently, Li et al.98 have reported the fabri-
cation of a BiOCl nanoake lm perpendicular to the stainless
steel (SS) substrate by the hydrolysis of BiCl3 in ethanol solu-
tion. When modied with the 1H,1H,2H,2H,-peruorodecyltri-
chlorosilane (FDTS), the BiOCl lm exhibited excellent
superhydrophobicity and the water contact angle could reach as
high as 169 .
To solve the energy crisis, photovoltaic systems based on
semiconductor materials have paved the path for the
construction of new alternative photoelectrochemical cells
(PEC). Among the BiOX (X ¼ Cl, Br and I) series, BiOI is
undoubtedly the most promising candidate for solar cell
materials due to its low cost, strong visible light absorption and
lower band gap (ca. 1.7 eV). Zhang et al.101 reported the synthesis
Fig. 5 Schematic illustration of the fabrication of flower-like BiOCl
hierarchical nanostructures by an in situ oxidation process.82 Reprinted
with permission from Wiley-VCH.
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of BiOI ake arrays on FTO glass by successive ionic layer
adsorption and reaction (SILAR) method. The prepared BiOI
nanoake array solar cell showed highly enhanced photovoltaic
performance than the annealed TiO2/FTO one, and could reach
the maximum incident photo-to current conversion efficiency
(IPCE) value of 4%. Very recently, Mullins et al.102 have synthe-
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sized BiOI nanoplatelet photoelectrodes by spray pyrolysis on
FTO substrate. As displayed in Fig. 6, the thickness of BiOI
nanoplate lms is approximately 1 mm. Intriguingly, the BiOI
lm exhibits n-type conductivity, and its maximum IPCE
exceeds over 20% in the visible range for the oxidation of I to
I3 at 0.4 V vs. Ag/AgCl in acetonitrile. Such ndings could
expand the photovoltaic application of BiOX nanomaterials and
allow their potential use in photoelectrochemistry.
3. Hybridization of BiOX
photocatalysts with other materials
Apart from the effect of size and shape, the catalytic property can
also be tuned by varying the composition and support of a
nanocatalyst. For heterogeneous photocatalysis, due to their
intrinsic features such as wide band gap or photo-induced
corrosion, single component catalysts (e.g., TiO2, CdS) are inca-
pacitated for large scale practical applications. Therefore, in
order to tackle these issues and fulll the required demands,
hybrid photocatalysts, which are usually built by one or more
active components and a functional support, such as CdS–Au–
TiO2,115 Ag/AgCl,116 and TiO2/graphene,117 have been well devel-
oped. Such hybrid photocatalysts integrate the synergistic effects
of the individual species,118,119 which could endow the composite
systems with increased light harvesting, prolonged lifetime of
carriers, enhanced catalytic performance as well as higher
chemical stability. Generally, the BiOX-based (X ¼ Cl, Br, I)
hybrid photocatalysts can be divided into three categories
according to the type of newly added species (Table 2): (1)
semiconductor/BiOX hybrids,120–152 (2) metal/BiOX hybrids,153–160
and (3) sensitized BiOX hybrids.161–170
3.1 Semiconductor/BiOX composites
In contrast to one individual semiconductor photocatalyst,
semiconductor composites are more intriguing for their inter-
facial heterostructures, which are formed at their junctures and
Fig. 6 (a) SEM image of BiOI film deposited on FTO-coated glass
substrates. (b) IPCE spectrum recorded at 0.4 V vs. Ag/AgCl for the
BiOCl film with a peak light intensity of 476 mW cm2.102 Reprinted with
permission from American Chemical Society.
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have an important effect on their photocatalytic performances.
In terms of the band positions, there are usually three types of
semiconductor heterojunctions: straddling gap (type I), stag-
gered gap (type II) and broken gap (type III), as presented in
Fig. 7. Among them, semiconductor composites with the stag-
gered gap (type II) are the most studied in the eld of hetero-
geneous photocatalysis.3,12 In this case, the photoinduced
electrons and holes are easily separated between the two
semiconductors via effective interfacial charge transfer, thereby
boosting the photocatalytic performance of the semiconductor
composites.
Restricted by its wide band gap (ca. 3.46 eV), BiOCl works
only under UV light. Hence, by coupling with semiconductors
with suitable band gaps, the as-formed BiOCl/narrow band gap
(NBG) semiconductor composites could expand their photo-
absorption into visible light range. By chemical etching of
commercial Bi2O3 with hydrochloric acid (HCl), Lee et al.120
prepared BiOCl/Bi2O3 heterojunction structure. In this hybrid
system, BiOCl works as the main photocatalyst, which shows
strong oxidation ability towards gaseous 2-propanol and
aqueous 1,4-terephthalic acid decomposition, while Bi2O3
seems to perform as the sensitizer to absorb visible light. Due to
the formed heterojunction structure between them, the photo-
generated carriers can be separated efficiently and participate in
the subsequent photocatalytic oxidation process, leading to the
superior photocatalytic activity of the BiOCl/Bi2O3 composites
to that of P25. Besides this, other binary or ternary composites,
such as WO3/BiOCl,121 Fe3O4/BiOCl,122 NaBiO3/BiOCl,123 WO3/
BiOCl/Bi2O3,124 BiOCl/BiNbO4/TiO2,125 BiOCl/bismuth oxy-
hydrate,126 BiOCl/BiOBr,127 and BiOI/BiOCl128,129 have been
prepared and turned out to be efficient visible light-driven
photocatalysts.
For NBG semiconductors, quantum connement occurs
obviously when their sizes reduce to several to tens of nano-
meters.171 In this condition, the band structure of a semi-
conductor becomes discrete, along with the band gap
broadening to harvest solar light, which may allow one to tailor
the light absorption by combination with BiOX (X ¼ Cl, Br, I)
semiconductors. As expected, our group has designed and
prepared a novel efficient Bi2S3 nanocrystal (NC) sensitized
BiOCl hybrid photocatalyst by anion exchange.130 The anion
exchange takes place between BiOCl architectures and sulfur-
containing sources (i.e., thiourea, L-cysteine and thiacetamide)
in aqueous solution, which is based on the solubility difference
of BiOCl (Ksp ¼ 1.8  1031) relative to Bi2S3 (Ksp ¼ 1.0  1097).
Moreover, derived from the reactivity variance of the different
sulfur sources, Bi2S3 NCs with tunable sizes (3.1–8.5 nm) could
be obtained by an ion exchange reaction, thus regulating the
light absorption of the Bi2S3/BiOCl hybrid across the visible
light region. Evaluated by the decomposition of 2,4-dichlor-
ophenol (2,4-DCP) solution under visible light irradiation, the
as-prepared Bi2S3/BiOCl hybrid exhibited highly efficient pho-
tocatalytic activity and was dependent on the size of the Bi2S3
NCs. As illustrated in Fig. 8, the formed heterostructure by ion
exchange favors the interfacial charge transfer, which is further
conrmed by the band gap calculations. When the size of
the Bi2S3 NCs decreases, quantum connement makes the
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Table 2 Recent studies on BiOX-based hybrids (X ¼ Cl, Br, I) and their photocatalytic applications

Hybrid photocatalysts Synthetic procedure Photocatalytic results Ref.

Semiconductors composites
BiOCl/Bi2O3 Chemical etching 5.7 times 2-propanol decomposition rate that of P25 (Vis) 120
WO3/BiOCl Impregnation 40 times higher RhB degradation rate than that of P25 (Vis) 121
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Fe3O4/BiOCl Phase-transfer 100% RhB degradation within 40 min (Vis) 122

NaBiO3/BiOCl Chemical etching Higher RhB photodegradation rate than that of pure 123
NaBiO3 and BiOCl samples (Vis)
WO3/BiOCl/Bi2O3 Chemical etching and 1.3 times 2-propanol decomposition rate 124
incipient wetness that of N-doped TiO2 (Vis)
BiOCl/BiNbO4/TiO2 In situ precipitation Higher RhB degradation rate than that of BiOCl and BiNbO4 (Vis) 125
BiOCl/bismuth oxyhydrate Hydrothermal synthesis 5 times RhB removal rate larger than that on P25 (Vis) 126
BiOCl/BiOBr Solvothermal synthesis Higher RhB degradation rate than that of single 127
BiOCl and BiOBr (Vis)
BiOCl/BiOI Hydrothermal synthesis Higher MO and RhB degradation rate than that of 128
single BiOCl and BiOI (Vis)
BiOI/BiOCl Solvothermal synthesis 4 times bisphenol-A degradation rate that of pure BiOI (Vis) 129
Bi2S3/BiOCl Ion exchange 13 times 2,4-DCP decomposition rate faster 130
than that of N-doped P25 (Vis)
Bi2S3/BiOCl Ion exchange Higher RhB degradation rate than that of 131
single BiOCl, Bi2S3 and P25 (Vis)
Bi2S3/BiOI Ion exchange 81.9% MO degraded within 5 h (Vis) 132
AgI/BiOI Chemical bath 3 times phenol decomposition rate higher than that of BiOI (Vis) 133
AgI/BiOI Ion exchange About 3 times 2,4-DCP decomposition rate faster than 134
that of AgI/BiOI synthesized by chemical bath method (Vis)
AgI/BiOI Ion exchange 7.8 and 3.0 times higher than that of bare BiOI 135
and AgI, respectively (Vis)
AgBr/BiOBr Co-precipitation 100% RhB degradation within 30 min (Vis) 136
BiOBr/Bi2WO6 Hydrothermal synthesis Almost 100% RhB degradation within 40 min (Vis) 137
BiOBr/bismuth oxyhydrate Hydrothermal synthesis 10.7 times RhB removal rate higher than that on P25 (Vis) 138
BiOI/BiOBr Deposition–precipitation Higher MO degradation rate than that of single BiOI and BiOBr (Vis) 139
BiOBr/C3N4 Deposition–precipitation 1.5- and 48.9-fold RhB degradation rate faster 140
than those over BiOBr and C3N4, respectively (Vis)
g-C3N4/BiOBr Solvothermal synthesis 87% RhB degraded within 30 min (Vis) 141
BiOI/TiO2 So-chemical method 95% MO degradation within 2 h (Vis) 142
BiOI/TiO2 Impregnating–hydroxylation 3 times MO degradation rate faster than that of BiOI lm (Vis) 143
ZnO/BiOI Chemical bath Enhanced MO degradation rate than ZnO and BiOI (Vis) 144
ZnWO4/BiOI Chemical bath 86% MO degradation within 4 h (Vis) 145
BiOI/ZnTiO3 Precipitation–deposition 9.8 and 11.1 times Rh 6G degradation higher 146
than that of BiOI and ZnTiO3, respectively (Vis)
BiOI/(BiO)2CO3 Chemical etching Enhanced MO degradation than their individual counterparts (Vis) 147
Bi2O2CO3/BiOI Co-precipitation 8 times higher RhB degradation rate than that of BiOI (Vis) 148
BiOI/Bi2O3 Chemical etching 3.9 times phenol decomposition rate that of Bi2O3 (Vis) 149
Bi4Ti3O12/BiOI Successive ionic layer Highly enhanced RhB degradation and phenol 150
adsorption and reaction decomposition than Bi4Ti3O12 (Vis)
C3N4/BiOI Chemical bath About 4.2 and 5.3 times faster than that of C3N4 151
and BiOI, respectively. (Vis)
BiOBr/ZnFe2O4 Precipitation–deposition 100% MO degraded within 40 min (Vis) 152

Metal/Semiconductor hybrids
Pt/BiOI Photodeposition 90% acid orange II degradation within 1 h (Vis) 153
Bi/BiOCl UV light-induced chemical 4.8 times MO degradation rate that of BiOCl (UV) 154
reduction
Ag/BiOI Photodeposition 4 times larger acid orange II degradation rate than that of BiOI (Vis) 155
Ag/Ti-doped BiOBr Chemical reduction; 3 times RhB degradation rate that of the Ti-doped BiOBr (Vis) 156
photoreduction;
solvothermal reduction
Ag/BiOBr Precipitation–deposition Decreased RhB degradation rate than that of primitive BiOBr (Vis) 157
Ag/AgBr/BiOBr Ion exchange and 56 times MO degradation rate faster than that of N-doped P25 (Vis) 158
photoreduction
Ag/AgCl/BiOCl Chemical bath Completely degrade RhB within 30 min (Vis) 159
Ag/AgX/BiOX Chemical bath Ag/AgCl/BiOCl: 12 times that of Ag/AgCl; Ag/AgBr/BiOBr: 160
(X ¼ Cl, Br) 7 times that of Ag/AgBr (Vis)

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Table 2 (Contd. )

Hybrid photocatalysts Synthetic procedure Photocatalytic results Ref.

Co-catalyst or sensitizer modied hybrids

Graphene/BiOCl Solvothermal synthesis 2 times larger methylbenzene degradation rate 161
than that on BiOCl (UV)
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BiOBr/graphene Solvothermal synthesis 2 times NO removal rate that of BiOBr (Vis) 162
BiOBr/graphene Solvothermal synthesis 3 times RhB degradation rate higher than that of BiOBr (Vis) 163
BiOBr/graphene Microwave-assisted Almost 100% MO degraded within 80 min (Vis) 164
solvothermal
synthesis
BiOI/graphene Hydrothermal synthesis 6 times higher MO degradation rate than that of BiOI (Vis) 165
BiOI/MWCNT Solvothermal synthesis Complete AOII degradation within 3 h (Vis) 166
BiOI/[Bmim]I IL Chemical bath Enhanced MO degradation rate than that on BiOI (Vis) 167
MnOx/BiOI Photo-deposition 78.8% RhB degradation within 30 min (Vis) 168
BiOCl/phthalocyanine copper Liquid loading 76 times photocurrent intensity higher than that of 169
bare BiOCl electrode under simulated sunlight
Bin(Tu)xCl3n/BiOCl Hydrolysis 13 times higher RhB degradation rate than that on BiOCl (Vis) 170

Br, I)130–132 and even other Bi-based semiconductors with Bi2S3

Fig. 7 Schematic diagram of three types of semiconductor
heterostructures.
Fig. 8 Schematic illustration of band energy positions and the charge
transfer process of the Bi2S3 NCs/BiOCl hybrid under visible light
irradiation.130 Reprinted with permission from the Royal Society of
Chemistry.
NCs modication, which allows tunable solar light harvesting
and photocatalytic efficiency enhancement.
In view of highly efficient photocatalysts working under
visible light, the semiconductor composites constructed by two
visible light responsive semiconductors with staggered band
potentials sounds more promising and meaningful. Our group
has rst developed the novel nanostructured AgI/BiOI semi-
conductor composites by a chemical bath method.133 Compared
to BiOI (1.73 eV) and AgI (2.8 eV), the as-prepared AgI/BiOI
composites displayed greatly enhanced photocatalytic activities
towards MO dye degradation and phenol decomposition under
visible light irradiation. According to the band gap calculations,
AgI and BiOI have staggered band potentials, in accordance
with the type II heterostructure, which favors the interfacial
charge transfer. Meanwhile, as the CB edge of AgI (0.55 eV) is
more negative than that of BiOI (0.58 eV), the stability of AgI is
also ensured by the interfacial transfer of the photo-induced
electrons from AgI to BiOI, preventing its combination with the
interstitial Ag+ to engender metallic Ag0. This work illustrates
that AgI/BiOI composites could be used as stable and efficient
visible-light-driven photocatalysts. Yet, precipitation of AgI NPs
on BiOI nanoplates inevitably brings about poor dispersity and
loose contact between them, which goes against the separation
of the photo-generated carriers. Very currently, we have opti-
mized the synthetic procedure and prepared 3D hierarchical
AgI/BiOI hybrids, which consist of AgI NPs uniformly anchored
on the BiOI nanosheets.134 To fulll this target, a facile ion
exchange reaction in EG between BiOI hierarchical micro-
spheres and AgNO3 was adopted, as presented in eqn (1) below.

BiOI + Ag+ / AgI + BiO+ (1)

Bi2S3/BiOCl hybrids absorb less visible light; while the CB of
Bi2S3 moves to more negative potentials to result in a larger CB
energy difference between BiOCl and Bi2S3, which favors the
electron transfer. Consequently, the optimized case is observed
for the Bi2S3/BiOCl hybrid with Bi2S3 size of about 4.7 nm,
which shows the best photocatalytic performance. This
synthetic strategy could be generally applied to BiOX (X ¼ Cl,
With the addition of PVP surfactant, the sizes of AgI NPs
were tailored ranging from 55 to 16 nm. As shown in Fig. 9, the
AgI/BiOI hierarchical hybrids displayed much higher photo-
catalytic performances with respect to AgI, BiOI and AgI/BiOI
composites in decomposition of 2,4-DCP under visible light
irradiation. Furthermore, smaller AgI NPs are more active than

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Fig. 9 (a) Photocatalytic decomposition of 2,4-DCP solution over
different samples under visible light irradiation; (b) the photocatalytic
efficiencies of the AgI/BiOI hybrids versus the particle size of AgI under
visible illumination for 1 h; (c) scheme of the charge transfer process of
the AgI/BiOI hybrids exposed to visible light.134 Reprinted with
permission from the Royal Society of Chemistry.
larger ones, thus leading to the size-dependent photocatalytic
properties of the AgI/BiOI hybrids. The closer interfacial contact
and more surface reactive sites were considered to be associated
with the highly efficient photocatalytic activity of AgI/BiOI
hierarchical hybrids. In addition to the above-mentioned shape-
and size-dependence, the relative amount of AgI in AgI/BiOI
hybrids also plays an important role in determining their pho-
tocatalytic performances and the optimal value is observed at
70.4%.135 Other binary semiconductor composites including
AgBr/BiOBr,136 BiOBr/Bi2WO6,137 BiOBr/bismuth oxyhydrate,138
BiOI/BiOBr139 and BiOBr/C3N4,140,141 have also been reported to
exhibit enhanced visible light photocatalytic activities for
harmful organics removal.
Apart from type II heterostructure photocatalysts, another
important category of semiconductor composites is p–n junction
photocatalysts. The p–n junction is formed at the juncture
between n-type and p-type materials when they are placed in
contact with each other. Because the electron concentration in
the n-type material is much higher than that in the p-type
material, the electrons will migrate to diffuse across the junction
to the p-type material. Correspondingly, holes will diffuse from
the p-type to the n-type material. As a consequence, the formed
local electrostatic eld in p–n junction photocatalysts is favorable
for the separation of the photo-induced electrons and holes, thus
resulting in their enhanced photocatalytic activities.172,173 As is
known, BiOX (X ¼ Cl, Br, I) exhibits the PEC properties of p-type
semiconductors,174 which offers the opportunity to construct p–n
junction photocatalysts. In particular, BiOI with the smallest
band gap (1.7 eV) is more attractive and could serve as an
efficient visible light sensitizer for n-type semiconductors with
wide band gaps. So far, a number of BiOI-based p–n junction
photocatalysts, which involves BiOI/TiO2,142,143 ZnO/BiOI,144
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Fig. 10 Schematic diagrams for (A) energy bands of p-BiOI and n-TiO2
before contact and (B) the formation of a p–n junction and its energy
band diagram at equilibrium and transfer of photoinduced electrons
from p-BiOI to n-TiO2 under visible-light irradiation.143 Reprinted with
permission from American Chemical Society.
ZnWO4/BiOI145 and BiOI/ZnTiO3,146 BiOI/(BiO)2CO3,147,148 BiOI/
Bi2O3,149 Bi4Ti3O12/BiOI150 and C3N4/BiOI,151 have been prepared
and displayed highly enhanced visible light photocatalytic activ-
ities. Taking the BiOI/TiO2 photocatalyst142,143 for example, the
schematic band diagram is illustrated in Fig. 10. Before contact,
the CB edge and Fermi level of BiOI are lower than those of TiO2.
Aer contact, the Fermi level of BiOI moves up while the Fermi
level of TiO2 moves down until the nal equilibrium state is
formed, along with the corresponding band edges shi. As a
result, the p-type BiOI/n-type TiO2 junction is formed, and the CB
edge of BiOI is higher than that of TiO2. Upon visible light irra-
diation, the excited photoelectrons on the CB of p-type BiOI
would migrate to that of n-type TiO2, while leaving holes on the
VB of BiOI. Thus, the light-induced electron–hole pairs would be
effectively separated by the formed interfacial p–n junction, and
leads to the highly enhanced photocatalytic activity towards MO
degradation and PEC response of BiOI/TiO2 semiconductor
composites. Different from using p-type BiOI as the visible light
absorbing agent, Kong and co-workers152 have employed an
n-type ZnFe2O4 (1.67 eV) to sensitize p-type BiOBr (2.88 eV).
The as-prepared BiOBr/ZnFe2O4 photocatalyst exhibited
enhanced degradation of RhB dye solutions under visible light,
which is attributed to the interfacial p–n junction that facilitates
the charge transfer. From these results, it demonstrates that the
photocatalytic efficiency of the semiconductor composites can
also be dramatically improved by the formation of a p–n junction,
which is crucial for the design and exploitation of highly efficient
photocatalyst systems.
3.2 Metal/BiOX hybrids
To inhibit the recombination of the photo-induced carriers, one
alternative is to load noble metal nanoparticles (e.g., Au, Ag, Pt)
on the surface of semiconductors, which could favor the inter-
facial charge transfer and promote the photocatalytic perfor-
mances of the metal/semiconductor hybrids.11,175 Because BiOX
(X ¼ Cl, Br, I) exhibit p-type conductivity, their Fermi levels are
generally lower than that of noble metals. Aer contact, the holes
of BiOX will migrate to the noble metal until their Fermi levels are
pulled to the same position, and as a consequence the Schottky
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Fig. 11 Schematic diagram illustrating two types of charge transfer
process for metal/p-type semiconductor hybrid photocatalysts: (a)
metal as the electron trap center and electrons from excited p-type
semiconductor to metal, (b) electron transfer from excited noble metal
due to LSPR to p-type semiconductor.
barrier for holes at the interface will be formed, as shown in
Fig. 11a. When BiOX (X ¼ Cl, Br, I) semiconductors are excited by
light with energy above their band gap (Eg) values, the photo-
generated electrons would accumulate on the metal NPs that
serve as trap centers, leaving holes on the BiOX semiconductor,
so that the interfacial charge transfer substantially promotes the
photocatalytic performances of the metal/BiOX hybrids. For
example, Yu et al.153 deposited Pt NPs on the BiOI nanoplates and
found the Pt/BiOI hybrid showed higher visible light photo-
catalytic degradation performance towards acid orange II than
pure BiOI. By using a UV-induced chemical reduction route, Liu
and co-workers154 prepared a Bi/BiOCl hybrid photocatalyst,
which displayed much higher MO degradation performance and
transient photocurrent responses compared to the pure BiOCl
sample. The presence of metallic Pt or Bi NPs is crucial for the
photocatalytic activity enhancement of the hybrids, which
perform as the electron reservoir and thus accelerate the inter-
facial charge transfer between metal and BiOX semiconductors.
On the other hand, the interaction between noble metal NPs
(i.e. Au and Ag) and incident light with considerable energy could
give rise to the collective oscillation of free electrons, which is
known as localized surface plasmon resonance (LSPR).176–178 As
presented in Fig. 11b, upon exposure to visible light, the electrons
would transfer from the photo-excited noble metal NPs to the
conduction band of BiOX (X ¼ Cl, Br, I) semiconductors, leaving
holes in the noble metals. This electron transfer path is opposite
to the case mentioned above, in which the BiOX semiconductor is
excited by light and the photo-induced electrons on the CB
migrate to the noble metal NPs. In fact, when the metal/semi-
conductor hybrid is comprised of a plasmonic noble metal and a
visible-light-sensitive semiconductor, both of the electron trans-
fer processes are present and competitive. Thus, under visible
light irradiation, enhanced photocatalytic performance is found
on Ag/BiOI155 and Ag/Ti-doped BiOBr photocatalysts,156 while the
contrary decreased effect is also observed on the Ag/BiOBr
photocatalyst.157
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Fig. 12 (a) The synthetic strategy of the Ag/AgBr/BiOBr hybrid. Typical
SEM images of (b) BiOBr, and (c) Ag/AgBr/BiOBr hybrid photo-
catalyst.158 Reprinted with permission from the Royal Society of
Chemistry.
To develop highly efficient photocatalysts working under
visible light, it usually involves the integration of the hetero-
structured semiconductor/semiconductor composites and
plasmonic metal/semiconductor hybrids. Recently, our group
has reported a novel Ag/AgBr/BiOBr hybrid photocatalyst, which
displayed highly efficient photocatalytic activities in the steril-
ization of pathogenic organism and degradation of organic
dye.158 As shown in Fig. 12, such three-component hybrid was
prepared through in situ ion exchange reaction between hier-
archical BiOBr microspheres and Ag+ out of AgNO3 in EG
solution, as shown in eqn (2).
BiOBr + Ag+ / AgBr + BiO+ (2)
The AgBr NPs were then partially reduced to metallic Ag0
upon visible light illumination, and the resulting Ag/AgBr NPs
were 20–50 nm in size and uniformly anchored on BiOBr
microspheres. Under visible light irradiation, the Ag/AgBr/
BiOBr hybrid could deactivate the Escherichia coli (E. coli)
bacteria in less than 10 min and bleach the MO dye in only 4
min, which is superior to N-doped P25 by a factor of 56. The
plasmon-induced oscillation processes of Ag0 NPs upon light
irradiation enable the Ag/AgBr/BiOBr hybrid to harvest light in
the vis-NIR region and transfer the interfacial photo-excited
electrons efficiently, thus ensuring the excellent activity and
good stability of the hybrid. Followed by this work, Ag/AgCl/
BiOCl hybrids159,160 were also prepared and showed enhanced
visible-light photocatalytic activity.
3.3 Co-catalyst or sensitizer modied hybrids
To expedite the separation of the photo-induced carriers on a
semiconductor upon light excitation, proper co-catalysts (e.g.,
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Fig. 13 Schematic illustration of the visible light photocatalytic
enhancement of BiOBr/graphene nanocomposites.162 Reprinted with
permission from American Chemical Society.
NiOx, RuO2 and graphene)2,3,29 are usually introduced to
promote its corresponding photocatalytic performances. The
co-catalyst could perform as reaction sites, and accelerate the
interfacial charge transfer between it and the light-harvesting
semiconductor. Therefore, one can tailor the photocatalytic
performances of BiOX (X ¼ Cl, Br, I) semiconductors by
loading proper co-catalysts. For instance, graphene, which is a
new carbon material with excellent electron mobility, has been
employed for hybridization with BiOX (X ¼ Cl, Br, I) and
showed rather improved photocatalytic efficiencies.161–165 Ai
and co-workers162 have synthesized BiOBr/graphene hybrids
through a solvothermal route using graphene oxide (GO),
bismuth nitrite, and CTAB as the precursors. As shown in
Fig. 13, BiOBr nanoplates with hundreds of nanometers are
dispersed randomly on the 2D graphene sheet scaffold. Eval-
uated by the removal of gaseous NO under visible light irra-
diation, the as-prepared BiOBr/graphene hybrid displays a 2
times faster rate than that of BiOBr. The strong chemical
bonding between BiOBr and graphene is considered to facili-
tate the fast transportation of photogenerated electrons from
BiOBr to graphene, thus inhibiting the unwanted recombina-
tion and leading to its enhanced photocatalytic activity. In
addition to graphene, multi-walled carbon nanotubes
(MWCNT)166 and [Bmim]I IL167 as electron-trap species, while
MnOx168 as hole-trap species could also be used to separate the
photo-excited carriers and enhance the visible light photo-
catalytic activity of the BiOI semiconductor.
Analogous to TiO2, BiOCl is also a WBG semiconductor that
only responds to UV light. Aside from coupling with NBG
semiconductors, an alternative to harvesting visible light
absorption of the BiOCl semiconductor is modication with
photosensitizers.169,170 For example, Wang et al.169 employed
phthalocyanine copper (CuPc) to photosensitize BiOCl via
liquid loading. The prepared BiOCl/CuPc has strong visible
light absorption (500–800 nm) and displays 76 times photo-
current intensity higher than that of a bare BiOCl electrode
under simulated solar light. Interestingly, in a methanol–
H2O–RhB system, overall water splitting was realized on the
BiOCl/CuPc hybrid. This may provide a prospective method
for solar energy storage and conversion, though the activity is
very low.
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4. Structural design of BiOX
photocatalysts
In addition to the microstructure modication and hetero-
structure hybridization, structural design also plays a crucial
role in determining the performances of the photocatalysts. By
virtue of the structure–property correlation, the optical and
catalytic properties of one inorganic semiconductor material is
dependent on their structures, which involves crystal, elec-
tronic, phase and surface structures. Therefore, one can boost
or maximize the photocatalytic performances of the photo-
catalysts by structural design, such as doping, solid solution
formation, and composition tailoring.
4.1 Doping or defect introduction
The optical property of one material is dependent on its
underlying electronic and band structures, which could be
tuned by doping of foreign atoms or introduction of defects.12,179
On the basis of the DFT calculations on the electronic structures
of BiOX (X ¼ Cl, Br, I),180,181 Bi 6p orbitals dominate the CB,
while both O 2p and X np (n ¼ 3, 4, and 5 for X ¼ Cl, Br, and I,
respectively) orbitals contribute to the VB. Moreover, as the
atomic number of X increases, the density peak of X np states in
the valence band moves towards the VB top, leading to the
decreasing band gap from BiOCl to BiOI. It is desirable that
aer doping, the merits of the BiOX (X ¼ Cl, Br, I) host materials
are maintained and favorable changes in its electronic structure
could be engendered.
To date, metal (e.g., Mn, Fe, Ti)182–185 and non-metal
(e.g., I)186–188 ions have been reported to dope into BiOX nano-
materials. For example, because of the similar ionic radius of
Mn2+ (0.080 nm) with respect to Bi3+ (0.096 nm), Mn ions can be
incorporated into BiOCl.182 With red shi in its absorption edge,
the Mn-doped BiOCl (2.75 eV) product displayed enhanced
photocatalytic performance towards malachite green (MG)
degradation under halogen lamp irradiation. In contrast to
Fig. 14 (a) Gradual color changes of the as-prepared BiOIx powders.
(b) UV-vis diffuse reflectance spectra of self-doped BiOIx powders.186
Reprinted with permission from American Chemical Society.
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metal ion doping, non-metal anionic ion doping could effec-
tively form a new valence band to engineer the band gaps of
BiOX materials. Zhang et al.186 demonstrated that self-doping of
iodine in BiOI could tune its electronic and band structures,
which was also conrmed from DFT calculations. As shown in
Fig. 14, with increasing iodine content, the color of the products
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changes from orange to deep red. In the meantime, the UV-vis
diffuse reectance spectra of the BiOIx samples red shi
accordingly. The optimal case was found for BiOI1.5, which
showed the best photocatalytic performance for MO degrada-
tion and NO removal under visible light irradiation.
The introduction of vacancy (e.g., oxygen vacancy, metal
atom vacancy) under reducing atmosphere or thermal condi-
tions could also cause the variation of electronic structure,
charge transport and surface property of the semiconductor.
When exposed to UV irradiation with the protection of Ar gas,
the color of BiOCl can be changed from white to black, as dis-
played in Fig. 15.189 The black BiOCl product is endowed with
visible light response due to the formation of oxygen vacancies.
The oxygen vacancies could yield the defect state below the CB
of BiOCl, which perform as active electron traps and facilitate
the separation of photo-induced carriers, and thus lead to the
highly enhanced photocatalytic efficiency of the black BiOCl. In
addition to oxygen vacancy, metal atom vacancy also plays an
important role in the tuning of band structure and electronic
structure, and further photocatalytic activity of the semi-
conductor material. Very recently, Xie and co-workers190 have
prepared two types of BiOCl samples by hydrothermal
synthesis: BiOCl nanoplates (thickness of about 30 nm) and
ultrathin BiOCl nanosheets (thickness of 2.7 nm). With the
thickness of the nanosheets decreasing to the atomic scale, the
predominant defects change from isolated V000 Bi to triple associ-
ates V000 V $$ 000
Bi O BiV , which is conrmed by the positron annihilation
spectra. The presence of triple associates V000 V $$ 000
Bi O Bi brings the
V tion and VB potential, the highest photocatalytic activity is
ultrathin BiOCl nanosheets with effective separation of
Fig. 15 UV-vis diffuse reflectance spectra of the BiOCl samples. (B)
Band structure model and photoreaction process on black BiOCl.189
Reprinted with permission from the Royal Society of Chemistry.
2020 | Nanoscale, 2014, 6, 2009–2026
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Review
electron–hole pairs and more reductive photo-excited electrons.
Compared to BiOCl nanoplates, the ultrathin BiOCl nanosheets
display signicantly improved solar-driven photocatalytic
activity in RhB degradation.
4.2 Solid solutions
Different from doping of foreign atoms, which leads to isolated
energy states below CB or above VB, the formation of solid
solution could allow one to tune the band gaps of photocatalysts
continuously.3 In solid solution photocatalysts, their band gaps
can be narrowed by lowering the level of CB and/or liing the
level of VB, thereby tailoring the electronic structures to maxi-
mize their photocatalytic activities. For BiOX (X ¼ Cl, Br, I)
semiconductors, it has been reported that there is unlimited
solubility among them,191 and this offers the possibility to form
BiOX–BiOY (X, Y ¼ Cl, Br, I) solid solutions. Furthermore,
theoretical calculations illustrate that the alloying effect in the
solid solutions of BiOXs could greatly reduce the electron–hole
recombination.192 Therefore, the photocatalytic performances
of BiOX (X ¼ Cl, Br, I) semiconductors can be promoted by the
construction of solid solution photocatalysts.
Until now, a number of solid solution photocatalysts
(BiOCl1xBrx, BiOCl1xIx and BiOBr1xIx)193–200 have been
prepared by various methods. In 2007, Wang et al.193 used a so-
chemical method to synthesize a series of BiOClxI1x solid
solution photocatalysts. As presented in Fig. 16, the BiOCl1xIx
solid solutions display intense absorption in the visible light
region and their band gaps can be tuned in the range of 2.31–
1.98 eV with varying the x value from 0.2 to 0.8. Moreover, the
as-prepared BiOCl1xIx solid solutions exhibit enhanced visible
light photocatalytic activities with respect to the single BiOCl
and BiOI. Under the competition between visible light absorp-
observed for the BiOCl0.2I0.8 sample. Later, they also reported
the BiOBr1xIx solid solution photocatalysts,194 which also
showed promoted visible light photocatalytic performances
towards MO degradation with tunable band gaps. Recently, our
group196 has prepared BiOCl1xBrx solid solution photocatalysts
Fig. 16 UV-vis diffuse reflectance spectra of BiOCl1xIx photo-
catalysts. The inset shows the band gaps (Eg) of the samples at different
x.193 Reprinted with permission from Elsevier.
This journal is © The Royal Society of Chemistry 2014

Review
by the hydrothermal method. With the x value in the range of
0.2–0.8, the band gaps of BiOCl1xBrx solid solutions change
from 3.05 to 2.77 eV. Evaluated by RhB degradation and
2-propanol decomposition under visible light irradiation,
BiOCl1xBrx solid solutions display enhanced photocatalytic
efficiencies and the best case is found at BiOCl0.5Br0.5. From
Published on 22 November 2013. Downloaded by University of California - Los Angeles on 20/03/2018 13:51:21.
DFT calculations, it is demonstrated that the cation vacancies
VBi dominate the trapping center for photo-generated carriers.
4.3 Other bismuth oxyhalides
The composition and phase structure of semiconductor mate-
rials have great inuences on their optical, electronic and
photocatalytic properties. The original bismuth oxyhalides
belong to the Sillén family with a formula of [Bi2O2][Xm] or
[Bi3O4+n][Xm] (X ¼ F, Cl, Br, I; m ¼ 1–3), where the [Bi2O2] or
[Bi3O4+n] layers interlace with single, double or even triple
halogen layers.201 Besides BiOX (X ¼ Cl, Br, I), through altering
elements or compositions some other bismuth oxyhalides, such
as BiOF,202 Bi3O4Cl,203 Bi12O17Cl2,204 Na0.5Bi1.5O2Cl,205 CaB-
iO2Cl,206 PbBiO2Cl,207,208 Bi3O4Br,209 PbBiO2Br,210 Bi5O7I211–213
and Bi7O9I3,214,215 have been prepared and shown considerable
photocatalytic activities towards organic pollutant decontami-
nation. For example, Bi3O4Cl (2.79 eV) as a novel efficient
photocatalyst was obtained by a solid-state reaction between
Bi2O3 and BiOCl.203 As illustrated in Fig. 17, Bi3O4Cl is crystal-
lized in a layered structure with [Bi3O4] slabs alternating with
[Cl] slabs along the c-axis. In contrast to BiOCl, red shi in the
light absorption of Bi3O4Cl is observed due to its hybridized VB
of Cl 3p, O 2p and Bi 6s orbitals. To understand the effect of
band structure and VB potential on the photocatalytic effi-
ciency, Xiao et al.212 prepared a series of oxygen-rich bismuth
oxyhalides (i.e. BiOCl, Bi3O4Cl, BiOBr, Bi3O4Br, Bi4O5Br2, BiOI,
Bi5O7I, Bi7O9I3) by a hydrothermal route. They found that
different compositions of O : X (X ¼ Cl, Br, I) ratio could tailor
the VB composition and level of the bismuth oxyhalides, which
was further conrmed by DFT calculations. The prepared O-rich
BiOX compounds exhibit efficient visible-light-driven photo-
catalytic activities in the degradation of bisphenol-A. In partic-
ular, owing to their narrower band gaps and stronger oxidation
ability, Bi7O9I3 and Bi4O5I2 demonstrate superior activity to
other products.
Fig. 17 (a) The layered structure and (b) UV-vis diffuse reflectance
spectrum of Bi3O4Cl.203 Reprinted with permission from American
Chemical Society.
This journal is © The Royal Society of Chemistry 2014
View Article Online
Nanoscale
Extension of bismuth oxyhalides leads to the Sillén–Auri-
villius intergrowths [Bi2O2][An1BnO3n+1][Bi2O2][Xm], in which
the Aurivillius family [Bi2O2][An1BnO3n+1] alternates with the
Sillén family [Bi2O2][Xm].216 Recently, these combined bismuth
oxyhalides, such as Bi4NbO8Cl217 and Bi4TaO8Cl,218 have also
been reported to be novel efficient photocatalysts. For instance,
Lin et al.217 have prepared Bi4NbO8Cl (2.38 eV) by a solid state
reaction and observed its high photocatalytic performance in
MO degradation under visible light irradiation. The formula of
Bi4NbO8Cl can be denoted as [Bi2O2][NbO4][Bi2O2][Cl], where
2D [Bi2O2], [NbO4] and [Cl] slabs are stacked in sequence along
the c-axis to form the layered structure. The polarizing elds in
NbO6 and BiO8 local structures, as well as the internal electrical
elds between [Bi2O2] and [Cl] slabs are believed to promote the
separation of electrons and holes.
5. Summary and outlook
As a novel kind of bismuth-based layered semiconductor, BiOX
(X ¼ Cl, Br, I) have recently been of exceptional interest for their
considerable photocatalytic activities. To boost the visible-light-
driven photocatalytic performances of BiOX (X ¼ Cl, Br, I)
photocatalysts, numerous efforts have been done to expand the
light-response and expedite charge-transfer. Generally, three
dominant strategies have been adopted: (i) multi-length scale
microstructure modulation in the form of 1D templated nano-
bers, 2D intrinsic nanosheets, 3D assembled hierarchical
superstructure and supported thin lms; (ii) favorable hybrid-
ization with semiconductors, metals, and co-catalysts/sensi-
tizers; (iii) rational structural design by doping, solid solution
formation and composition tailoring. Notably, engineering
BiOX (X ¼ Cl, Br, I) nanostructures for efficient photocatalysis
usually requires the synergistic effect of several systems. For
instance, a three-component Ag/AgBr/BiOBr hybrid158 combines
the merits of a plasmonic Ag/AgBr photocatalyst and AgBr/
BiOBr composite photocatalyst, exhibiting greatly enhanced
visible light photocatalytic activities for the sterilization of
pathogenic organisms and degradation of organic dyes.
Despite much progress, the study of BiOX (X ¼ Cl, Br, I)
photocatalysts is still in its early stages, and additional chal-
lenges need to be addressed in future research. Conned by
their CB levels, BiOX (X ¼ Cl, Br, I) fail to fulll the requirements
to split water into H2. To date, most of the reports concerning
BiOX photocatalysts are focused on the decomposition of
organic pollutants. Other applications, such as CO2 reduction
and selective organic transformation, should be extended
utilizing BiOX photocatalysts.
Since the photocatalytic performance of a semiconductor is
dependent on its light-responsive range and carrier-separation
capacity, rational design of the BiOX-based complex architec-
ture systems (e.g., three-dimensional ordered inverse opals,219
non-symmetric Janus metal/semiconductor structure,220 metal/
insulator/semiconductor221) that meet the requirements is
crucial for constituting highly efficient and robust heteroge-
neous photocatalysts. For example, the periodic structures in
inverse opals could enhance its light harvesting by multiple
scattering, and the unintermitted pore tunnels would accelerate
Nanoscale, 2014, 6, 2009–2026 | 2021

Nanoscale
the separation of carriers, thereby making it a promising
candidate for next generation photocatalysis. Moreover, with
the aid of voltage bias, it is fascinating to study the photo-
electrocatalysis of BiOX, which facilitates the charge separation
and offers new opportunities to enhance their catalytic
properties.
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In the development of novel photocatalytic nanostructures,
chemical transformation of the existing material into another
demonstrates an effective and versatile synthetic strategy. As the
crystal structure of BiOX (X ¼ Cl, Br, I) is built by the interlacing
of [Bi2O2] slabs with double halogen slabs to form a layered
structure, such a strong ionic feature could allow ion exchange
reactions or lattice-directed topotactic transformations between
BiOX precursors and incoming species. By adopting this
method, a variety of well-dened nanostructures, such as
Bi2WO6 hollow microspheres,222 Bi2S3 super structured
networks,223–225 and Bi2E3 (E ¼ S, Se, Te) core–shell micro-
spheres226 can be obtained. The advent of nanoscience and
nanotechnology has brought great guidance and protocols to
develop highly efficient semiconductor photocatalysts. With
ever-growing in-depth investigations, it is anticipated that BiOX
(X ¼ Cl, Br, I)-based photocatalysts will be more efficient and
nd important applications in practical environmental
purications.
Acknowledgements
This work was nancially supported by the National Basic
Research Program of China (973 program, no. 2013CB632401)
and the National Natural Science Foundation of China (no.
21333006, 11374190, 51321091 and 21007031).
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