NANO: Brief Reports and Reviews

Vol. 13, No. 2 (2018) 1850016 (9 pages)

© World Scienti¯c Publishing Company
DOI: 10.1142/S1793292018500169

An Anion-Exchange Strategy to Bi2S3/Bi2O2(OH)(NO3)

Heterojunction with E±cient Visible Light
Photoreactivity

Jiawei Pang, Shenghuan Su and Qiaofeng Han*

Key Laboratory for Soft Chemistry and Functional Materials
Ministry of Education
Nanjing University of Science and Technology
by UNIVERSITY OF NEW ENGLAND on 02/17/18. For personal use only.

Nanjing 210094, P. R. China

*hanqiaofeng@njust.edu.cn

Received 4 December 2017

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Accepted 15 January 2018

Published 14 February 2018

As one of the basic bismuth nitrates, Bi2O2(OH)(NO3) (denoted as BION) has been reported to
exhibit powerful photodegradation activity for various contaminants. However, pure BION could
only be irradiated by UV light due to broad bandgap (
3.14 eV). Herein, Bi2S3/Bi2O2(OH)(NO3)
(denoted as BS-BION) heterojunction was prepared by an in situ ion exchange reaction between
BION and aqueous thiourea solution (pH  3). The resulting heterojunction possessed good
visible light absorption and closely contacted interfaces, which bene¯ted e®ective separation and
transfer of photogenerated charges, thus leading to excellent photocatalytic activity for the
degradation of rhodamine B (RhB) under visible light irradiation. Furthermore, the as-prepared
heterojunction photocatalyst also presented high photochemical stability, which may be of great
signi¯cance for practical application.

Keywords: Bi2S3/Bi2O2(OH)(NO3); heterojunction; anion-exchange; photocatalysis.

1. Introduction nitrate pentahydrate (Bi(NO3 Þ3 5H2O), basic bis-

Photocatalytic degradation is reported as a green,
sustainable and clean process for elimination of
contaminants and resolution of energy crisis. Bis-
muth-containing compounds, including Bi2O3,
Bi2MO6 (M ¼ Cr, Mo and W), BiVO4, BiOX
(X ¼ Cl, Br and I), BiPO4, (BiO)2CO3, and so on,
have been proposed as potential photocatalytic
materials in the degradation of pollutants and hy-
drogen evolution from water splitting due to e±-
cient visible light absorption compared to TiO2.1–10
In addition, as hydrolysis products of bismuth
muth nitrates ([Bi6O4þx (OH)4x ](NO3 Þð6xÞ  nH2O,
x ¼ 0–2; n ¼ 0–3), having about 15 kinds of di®er-
ent structures, were previously used for medical
applications and precursors of bismuth oxides,11–13
which have recently been drawing growing atten-
tion due to their rich chemical compositions, non-
toxicity and good photocatalytic activity. For
example, Liu's group synthesized [Bi6O6(OH)3]
(NO3)3  1.5H2O nanosheets by microwave-assisted
hydrothermal route, which exhibited excellent
photocatalytic activity for methyl orange (MO) and

1850016-1
 J. Pang, S. Su & Q. Han
malachite green degradation.14 Zhang et al. pre-
pared the multilayered meshing-teeth [Bi6O6(OH)3]
(NO3 Þ3 1.5H2O with predominant f110g facets by
hydrothermal method, which possessed high pho-
todegradation e±ciency for phenol.15 More recently,
our group synthesized [Bi6O6(OH)2](NO3 Þ4 2H2O
and [Bi6O5(OH)3](NO3 Þ5 3H2O at room tempera-
ture, which separately exhibited good photo-
catalytic and adsorptive properties for rhodamine B
(RhB) and MO.16 Another basic bismuth nitrate
([Bi2O2(OH)](NO3)), having di®erent composition
formula and structures from the above compounds,
have been reported by Huang's and our groups. This
compound is characterized by the layered structure
which could form a self-built electric ¯eld perpen-
dicular to the layers and thus favors the e±cient
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separation of photogenerated electron–hole pairs,
exhibiting superior photodegradation activity
against industrial contaminants, dyes and pharma-
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ceuticals.17,18 However, all of the photocatalytic
reactions were carried out under UV light irradia-
tion due to broad bandgap, which may restrict
practical application in photocatalytic degradation.
In addition, fast recombination of the photo-
generated electrons and holes in a single semicon-
ductor often leads to low quantum e±ciency.
Therefore, developing a facile strategy to extending
visible light response and enhancing photocatalytic
e±ciency of basic bismuth nitrates is of practical
signi¯cance.
In order to improve the performance of photo-
catalysts, several strategies have been reported,
such as defect engineering,19,20 ion doping, noble-
metal loading and narrow-bandgap semiconductor
sensitization.21–26 Among these, the fabrication of
heterojunctions has been demonstrated as one of the
most e±cient methods.21 For example, Bi2S3-sensi-
tized BiOCl and (BiO)2CO3 have been reported to
exhibit excellent visible-light-driven photocatalytic
activity.22–24 Bi2S3/ZnS heterojunctions also
showed enhanced adsorption capability and photo-
catalytic activity.25,26 Especially, for Sill
en type
compounds, they permit the exchange of the com-
ponent ions with exotic S 2 ions to engender the
heterojunctions with closely contacted interfaces,
which facilitate the interfacial charges transfer.
Owing to the layered structure of [Bi2O2(OH)]
(NO3) characterized by [Bi2O2] 2þ slabs interleaved
with OH  and (NO3 Þ  groups, herein, we demon-
strated a partial ion exchange strategy to prepare
Bi2S3/Bi2O2(OH)(NO3) (denoted as BS-BION)
1850016-2
heterojunction for the ¯rst time. Sulfur sources
played a crucial role in the photocatalytic perfor-
mance of the products. The BS-BION prepared
from thiourea (pH ¼ 3) presented the best visible-
light photoreactivity for degrading RhB and crystal
violet (CV).
2. Experimental Section
2.1. Materials and preparation
All the reagents were analytically pure, purchased
from commercial sources and used as received
without further puri¯cation. Deionized water was
used in all experiments.
Flower-like Bi2O2(OH)(NO3) (denoted as BION)
was prepared according to our previous work.17
Brie°y, 2 mmol of dried Bi(NO3 Þ3 was added into
5 mL of glacial acetic acid (HAc) solution and stir-
red for 1 h. After centrifugation to remove HAc, the
obtained solid was transferred into a 35 mL Te°on-
lined stainless steel autoclave with 30 mL deionized
water and heated at 150  C for 5 h. After the auto-
clave was cooled to room temperature automati-
cally, the white precipitate was collected by
centrifugation, washed several times with distilled
water and ethanol, and then dried under vacuum at
60  C for 10 h. The BS-BION heterojunction was
synthesized via a partial ion exchange route at room
temperature. Typically, BION (0.265 g, 0.5 mmol)
was added into 30 mL of thiourea solution (0.5 g,
6.5 mmol), and then, a few drops of HCl (1 M) was
added to promote the decomposition of thiourea.27
After stirring for 12 h, the brown solid was collected
by the same way as that of BION. A series of sam-
ples were prepared under various experimental
conditions by changing sulfur sources, reaction time
or solution pH in order to compare the e®ect of the
preparation conditions on the photocatalytic per-
formance of the heterojunctions.
2.2. Characterization
X-ray di®raction (XRD) was carried out on a Bruker
D8 Advance X-ray di®ractometer (CuK
radiation,
 ¼ 1:542 Å) at a scan rate of 0.05  2 s 1 . Trans-
mission electron microscopy (TEM) analysis was
conducted on a JEM 2100 (JEOL) microscope oper-
ating at 200 kV. X-ray photoelectron spectra (XPS)
were obtained on a Quantera II SXM X-ray photo-
electron spectrometer (PHI) with monochromatized
 An Anion-Exchange Strategy to Bi2 S3 /Bi2 O2 (OH )(NO3) Heterojunction

AlK
as the exciting source. The binding energies of
the elements were calibrated by using the C1s peak
at 284.8 eV in order to compensate for surface
charge e®ects. The speci¯c surface areas were
characterized by the nitrogen adsorption BET
method on a Micromeritics ASAP 2010 apparatus
and the samples were degassed at 200  C before
adsorption. UV-vis di®use re°ectance spectra
(DRS) were determined on a UV-2550 spectropho-
tometer (Shimadzu) equipped with an integrating
sphere, using BaSO4 as a reference.
2.3. Electrochemical and
photoelectrochemical property
The band positions of the catalysts were evaluated
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(BRAIC UV 1201). The photodegradation e±-
ciency was calculated by the ðC=C0 Þ  100%, where
C0 is dye concentration after adsorption–desorption
equilibrium, and C is the remnant dye concentra-
tion at a given irradiation time.
3. Results and Discussion
3.1. Structure, composition
and morphology
Since the solubility constant of Bi2S3 is very low
ðKsp ¼ 1:0  10 97 Þ,28 BION could transform to
Bi2S3 in the presence of S 2 ions, which could be
intuitively observed by the color change of the
composite from white to brown and ¯nally into

black as the ion-exchange time extended. XRD

through Mott–Schottky experiments on an electro- patterns of pure BION and the composite (BS-
chemistry workstation (CHI 760E, Shanghai BION) are shown in Fig. 1. The di®raction peaks of
Chenhua Instruments, China) at a constant fre-
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both BION and BS-BION could be indexed to or-

quency of 1000 Hz. The working electrode (photo- thorhombic Bi2O2(OH)(NO3) (ICSD 154359),17 and
anode) was prepared as follows: 20 mg of sample was no signi¯cant peaks assigned to Bi2S3 on the com-
mixed with 2 mL distilled water to form a slurry, posite BS-BION could be detected, implying that
then coated onto a 1 cm  1 cm °uorine-doped tin Bi2S3 was amorphous and low in content. The
oxide (FTO) glass substrate and dried at 80  C for change in lattice parameters was not detectable
10 h. A platinum plate and a saturated calomel after sul¯dation, which suggests that Bi2S3 existed
electrode (SCE) served as the counter electrode and only on the surface and did not insert the interlayers
reference electrode, respectively. 0.5 M Na2SO4 of BION.20
aqueous solution was employed as the electrolyte. The surface composition and chemical state of
Photocurrent response was measured on the elec- the as-prepared BS-BION were checked by XPS
trochemistry workstation in a similar way. A 500 W spectra. The survey spectra of BS-BION indicate
Xe lamp was used as the light source. the presence of Bi, O, N and C elements and no
obvious peak ascribed to S element could be ob-
2.4. Photocatalytic activity evaluation served due to low content [Fig. 2(a)]. Since the main
photoemission peak of S element (S 2p) is over-
The photocatalytic activity of the as-prepared
lapped with Bi 4f, XPS spectrum of S 2s was
samples was evaluated by photodegradation of RhB
and CV. The photocatalytic reaction was performed
in a XPA-7 photochemical reactor (Nanjing
Xujiang Machine-electronic Company, China). In a
typical photodegradation experiment, 20 mg of
photocatalyst was added into 50 mL of RhB solu-
tion (10 mg L 1 ). Before irradiation, the suspension
was stirred magnetically in the darkness for 1 h to
reach an adsorption–desorption equilibrium be-
tween the photocatalyst and dye. Then, the reaction
system was exposed to 500 W xenon lamp with a
420 nm cuto® ¯lter. During the photocatalytic re-
action, about 3 mL of suspension was sampled at
given time intervals, centrifuged to get rid of the
catalyst powders, and the remnant RhB was ana-
lyzed by using a UV-Vis spectrophotometer Fig. 1. XRD patterns of pure BION (a) and BS-BION (b).

1850016-3
 J. Pang, S. Su & Q. Han

(a) (b)
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(c) (d)

(e)

Fig. 2. XPS spectra of the as-prepared BS-BION: (a) survey, (b) S 2s, (c) Bi 4f, (d) O 1s and (e) N 1s.

recorded and a weak peak centered at 226.2 eV
could be observed, indicative of the presence of S 2
in the composite [Fig. 2(b)]. The high-resolution
XPS spectrum of Bi 4f shows two strong peaks
centered at 159.6 eV and 164.8 eV, which could be
respectively assigned to the 7/2 and 5/2 spin–orbit
of Bi 3þ [Fig. 2(c)]. The O 1s core level spectrum
could be deconvoluted into three peaks with the
binding energies at 530.5 eV, 531.4 eV and 532.6 eV
[Fig. 2(d)], which could be attributed to the oxygen
in Bi–O group, H2O and hydroxyl group, and NO  3,
respectively. The core level photoemission of N 1s

1850016-4
 An Anion-Exchange Strategy to Bi2 S3 /Bi2 O2 (OH )(NO3) Heterojunction
(a)
Fig. 3. TEM images of BION (a) and BS-BION (b and c).
shows one peak centered at 406.8 eV, which could be
ascribed to NO  3 anion [Fig. 2(e)]. Compared to
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single BION,17 the binding energies of Bi 4f, N 1s
and O 1s in BS-BION shifted a little toward higher
binding energies, suggesting that the interfacial in-
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teraction may exist between Bi2S3 and Bi2O2(OH)
(NO3).29
TEM observation shows that pure BION con-
sisted of nanosheet-based °ower-like hierarchical
structure [Fig. 3(a)], analogous to our previous
report.17 The adsorption of HAc on the surface of
Bi(NO3 Þ3 could enable Bi(NO3 Þ3 to hydrolyze into
Bi2O2(OH)(NO3) not into BiONO3. The formation
of the °ower-like Bi2O2(OH)(NO3) should be relat-
ed to its intrinsic layered structure characteristic as
well as suitable pH value due to HAc-adsorption.
The size and morphology of BS-BION did not ob-
viously change after sul¯dation except that the
particles were slightly aggregated. TEM observa-
tion shows that BS-BION consisted of °ower-like
morphology together with some scattered sheets
[Figs. 3(b) and 3(c)]. The appearance of sheets
should be due to mechanical stirring during sul¯-
dation which crumbled some of the °owers. In ad-
dition, a large amount of ultra¯ne nanoparticles
with an average diameter of about 10 nm appeared
on the surface of BION nanosheets [circled areas in
Fig. 3(c)], which should be Bi2S3 nanoparticles. In
view of color change of the samples and XPS results,
it could be concluded that Bi2S3 nanoparticles have
been formed on the surface of BION via a simple
in situ ion-exchange strategy.
The BET surface area of BS-BION was calcu-
lated to be 9.9 m2 g 1 according to N2 adsorption–
desorption isotherm curve, which is smaller than
that of pure BION (12.5 m2 g 1 ). The reduced sur-
face area for the composite may be caused by the
1850016-5
(b) (c)
particle aggregation due to long duration of the
sul¯dation reaction in solution.
3.2. Photocatalytic performance and
mechanism
RhB was ¯rstly used as a model compound to assess
the photocatalytic performance of the as-prepared
heterojunctions. Figure 4(a) indicates the temporal
spectra of RhB degradation over the as-prepared
BS-BION (produced the best results). About 40% of
RhB was adsorbed by BS-BION in the dark, and the
adsorption ability after sul¯dation was similar to
that of pure BION (35%).17 Upon visible light ir-
radiation, the maximal absorption peak intensity at
554 nm was decreased to 8% within 2.5 h. Simulta-
neously, the maximum peak gradually shifted from
554 nm to 517 nm, which could be ascribed to the
formation of N-deethylated RhB due to photosen-
sitization e®ect.
Figure 4(b) shows the photodegradation e±-
ciency of RhB with irradiation time over the het-
erojunctions obtained under various experimental
conditions. About 5% of RhB was photodegraded
in the absence of a photocatalyst within 2.5 h under
visible light irradiation, indicating that the pho-
tolysis of RhB may be negligible. Pure BION could
degrade only 7% of RhB due to its limited visible
light response (Eg ¼ 3:14 eV). While, about 92%
of RhB could be degraded within 2.5 h on the
BS-BION heterojunction prepared from thiourea
(pH ¼ 3).
The sulfur sources obviously in°uenced the pho-
tocatalytic activity of the composite BS-BION.
Under the same preparation conditions, the com-
posites prepared from thiacetamide (TAA) and
Na2S exhibited poor photocatalytic activity with
 J. Pang, S. Su & Q. Han

(a) (b)
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(c) (d)
Fig. 4. (a) Temporal UV-Vis spectra of RhB in aqueous BS-BION dispersions under visible light irradiation; (b) Photodegradation
e±ciency of RhB over the heterojunctions prepared from various sulfur sources (1. blank; 2. BION; 3. BION þ TAA (0.1 mmol) with
1 h of exchange reaction; 4. BION þ Na2S (0.1 mmol) with 1 h of exchange reaction; 5. BION þ Thiourea (6.5 mmol) with 24 h of
exchange reaction; 6. BION þ HCl (pH ¼ 3) þ Thiourea (6.5 mmol) with 12 h of exchange reaction); (c) Temporal UV-Vis spectra of
CV in aqueous BS-BION dispersions under visible light irradiation; (d) Photodegradation e±ciency of CV over the heterojunctions
prepared from various sulfur sources [samples 1–6 same with (b)] (color online).

degradation e±ciency of 8% and 10%, respectively
(not shown here). The release rate of S 2 ions from
either TAA or Na2S was too fast, leading to fast
growth and large size of Bi2S3 nanoparticles. As
a consequence, the composites exhibited poor pho-
tocatalytic activity because the Bi2S3 layers was
too thick on the surface of BION and may inhibit
the transformation of photogenerated carriers. Even
when the added TAA or Na2S amount was de-
creased from 6.5 mmol to 0.1 mmol and the reaction
time was shortened from 12 h to 1 h, the resulting
composites still exhibited poorer photodegradation
e±ciency than from thiourea [Fig. 4(b)]. These were
di®erent from the cases of Bi2S3/(BiO)2CO3 and
Bi2S3/BiOCl,22–24 where the composites prepared
from TAA or Na2S possessed higher photodegradation
e±ciency than from thiourea. The main reason
should be that the solubility constant of BION is
much higher than that of Bi2S3. BS-BION prepared
from thiourea (pH  3) exhibited the highest degra-
dation rate, which is about 26, 2 and 4 times higher
than pure BION, and the heterojunction prepared
from TAA and Na2S, respectively. Nevertheless, too
little amount of Bi2S3 could not e±ciently improve
the photocatalytic performance of BION. For ex-
ample, the decomposition of thiourea in the absence
of HCl was very slow and the degradation e±ciency
of RhB was only 88% even if the ion-exchange reac-
tion time was extended from 12 h to 24 h (not shown
here). Therefore, several drops of HCl (pH  3) was
added to accelerate the decomposition of thiourea.
The as-prepared heterojunction BS-BION also
exhibited photocatalytic activity for CV degradation
with an e±ciency of 40% within 2.5 h under visible

1850016-6
 An Anion-Exchange Strategy to Bi2 S3 /Bi2 O2 (OH )(NO3) Heterojunction
light illumination [Fig. 4(c)], higher than pure BION,
and the heterojunction prepared from TAA and Na2S
[Fig. 4(d)].
In order to demonstrate the photocatalytic per-
formance and exclude the photosensitizing process
of the as-prepared BS-BION, the photodegradation
of colorless pollutants like phenol and salicylic acid
(SA), which has no photosensitization e®ect, was
conducted under otherwise an identical condition
with RhB degradation. The results show that about
30% of phenol and 39% of SA were decomposed by
BS-BION within 5 h of visible light irradiation, sug-
gesting that the photodegradation of dyes is mainly
caused by direct semiconductor photocatalysis.
For practical application, the reusability and
stability of a photocatalyst are very important ex-
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cept for the photocatalytic activity. The recycling
experiment was conducted for RhB degradation on
BS-BION by four successive runs under visible light
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illumination. The result revealed that the photo-
reactivity of BS-BION was decreased by 20% after
four cycles (Fig. 5). This was probably induced by
the adsorption of RhB on the surface of the photo-
catalyst, which may cover the active centers of the
catalyst surface, as well as the loss of the photo-
catalyst in the experimental process. The XRD
pattern of BS-BION after four cycles appeared to be
similar to the fresh catalyst (not shown here), in-
dicating that the as-prepared BS-BION was stable
during the photocatalytic reaction.
3.3. Light absorption, electronic band
structure and mechanism
Light absorption property of the as-prepared sam-
ples was investigated by DRS spectra. As shown in
Fig. 5. Cycle experiment on BS-BION.
1850016-7
Fig. 6(a), black Bi2S3 prepared by extending ion
exchange time to 24 h using Na2S as sulfur source
exhibited intense absorption over the whole visible
range. White BION could only absorb UV light with
an absorption edge around 360 nm. As compared to
pure BION, light absorption of BS-BION was
broadened dramatically from UV to visible-light
region with a absorption band edge at 480 nm,
which is in good agreement with its brown color.
This was caused by the loading of Bi2S3 on the
surface of BION.23 The increased visible-light ab-
sorption of the composite BS-BION would facilitate
the e±cient utilization of visible light for generating
electron–hole pairs. The calculated direct bandgap
(Eg ) of Bi2S3 and indirect Eg of BION are 1.51 eV
and 3.14 eV, respectively. Herein, larger Eg value of
Bi2S3 nanoparticles than the reported bulk Bi2S3
(1.33 eV) could be attributed to quantum con¯ne-
ment e®ect due to smaller particle size.
In order to ascertain the band levels, the Mott–
Schottky plots were measured on an electrochemical
workstation. As revealed in Fig. 6(b), the positive
slope of the C 2 –E curves suggests that both BION
and Bi2S3 belonged to n-type semiconductors.16,28
The °at band potentials (Vfb ) of BION and Bi2S3
were derived by extrapolating the curves to x-axis,
which were estimated to be 0.45 V and 0.58 V
versus SCE (i.e., 0.21 V and 0.34 V versus NHE),
respectively. It is believed that the conduction band
potential minimum (ECB ) is 0.1 V more negative than
Vfb for an n-type semiconductor.30 The calculated
valence band edge potentials (EVB ) of BION-4N and
Bi2S3 based on the equation (ECB ¼ EVB  Eg ) are
2.83 V and 1.07 V versus NHE, respectively.
In order to explore the photocatalytic mecha-
nism involved in this system, the active species
trapping experiments were carried out by sepa-
rately adding the scavengers to the photoreaction
system under otherwise identical conditions with
RhB degradation without any scavengers. The ap-
parent reaction rate constant (kapp ) of BS-BION for
RhB degradation changed with various scavengers
is shown in Fig. 7. It indicates that kapp values de-
creased more signi¯cantly by adding benzoquinone
(BQ; a quencher of O 2 ) and ammonium oxalate
(AO; a quencher of h þ ) than by isopropanol (IPA; a
quencher of OH) compared with that without any
quenchers. The results suggest that the O 2 radi-
cals and photo-generated holes (h þ ) are the main
reactive species while the OH radicals play a minor
role in the photodegradation process.
 J. Pang, S. Su & Q. Han
(a)
Fig. 6. (a) DRS spectra of BION, Bi2S3 and BS-BION; (b) Mott–Schottky plots of BION and Bi2S3.
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Fig. 7. Trapping experiment in the presence of various
quenchers (1 mM) for RhB photodegradation on BS-BION.
Considering the band structures of the samples
and active species quenching results, a schematic of
the photocatalytic mechanism for the BS-BION
heterojunction is illustrated in Scheme 1. Bi2S3
could be excited by visible light to produce electrons
and holes, but these carriers might quickly be
recombined due to narrow bandgap in a single
Bi2S3. When Bi2S3 and BION were coupled to form
an intimate heterojunction, the photoelectrons
would move from CB of Bi2S3 to the more positive
Scheme 1. A schematic illustration of the energy band levels
for BS-BION heterojunction.
1850016-8
(b)
CB of BION while the holes remained in the VB of
Bi2S3. As a consequence, the photogenerated car-
riers could be separated e®ectively. As the CB of
BION (0.31 V) is more negative than the O2/O 2
potential (0.046 V versus NHE),16 the electrons in
the CB of BION could easily reduce O2 to generate
O 2 radicals. In the same time, the OH radicals
may be produced from O 2 radicals and electrons.
Both O 2 and OH radicals could oxidize RhB. In
addition, the holes in the valence band of Bi2S3 may
directly oxidize RhB into small molecules. Although
BET surface area of BS-BION is smaller than that
of pure BION, BS-BION possessed much higher
photoreactivity. The excellent visible-light photo-
reactivity of BS-BION could be attributed to the
loading of suitable amount of Bi2S3 on the surface,
thus resulting in extended visible-light response and
e±cient carriers separation.
The separation e±ciency of photogenerated car-
riers was further con¯rmed by transient photocur-
rent response over several on-o® cycles under
visible light irradiation.31 As displayed in Fig. 8,
almost no photocurrent could be observed on pure
BION electrode due to its broad bandgap. Both
Bi2S3 and BS-BION exhibited a current increase
upon visible light irradiation, and a quick reverse
back to the original state upon the removal of
visible light. However, di®erent from BS-BION, the
photocurrent density of Bi2S3 with the light on was
not stable and rapidly dropped, which may be
caused by fast recombination of the carriers. The
higher and more stable photocurrent density for BS-
BION means greater prohibitation for the recom-
bination of electron–hole pairs and thus better
 An Anion-Exchange Strategy to Bi2 S3 /Bi2 O2 (OH )(NO3) Heterojunction
Fig. 8. Transient photocurrent responses of BION, Bi2S3 and
BS-BION with visible light on/o®.
photocatalytic activity. Moreover, no photocurrent
decay was observed, indicating that BS-BION
electrodes possessed high separation e±ciency of
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photogenerated electrons and holes.
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4. Conclusions
In summary, Bi2S3/Bi2O2(OH)(NO3) (i.e., BS-
BION) heterojunction could be prepared by a par-
tially ion exchange method. BS-BION obtained by
using thiourea as a sulfur source at pH  3 pos-
sessed the best photocatalytic activity for RhB
degradation under visible light illumination. The
high photocatalytic activity could be attributed to
enlarged visible light response and e±cient separa-
tion of the photogenerated charge carriers due to
the construction of the heterojunction with intimate
interfaces via an in situ ion-exchange strategy. This
work demonstrated a facile route for developing
basic bismuth nitrates with visible-light-driven
photocatalytic activity which may become potential
photocatalysts in practical applications for envi-
ronmental remediation.
Acknowledgments
We gratefully acknowledge the National Natural
Science Foundation of China (51372117) for ¯nancial
support. Jiawei Pang and Shenghuan Su equally
contributed to this work.
Funding
The work is ¯nancially supported by the National
Natural Science Foundation of China (51772155).
1850016-9
Con°ict of Interest
The authors claimed that there is no con°ict of in-
terest involved in this manuscript.
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