Chemical Engineering Journal 228 (2013) 1110–1120

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Chemical Engineering Journal

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Enhanced photocatalytic activities of BiOI/ZnSn(OH)6 composites

towards the degradation of phenol and photocatalytic H2 production
Huiquan Li a,b, Yumin Cui a,⇑, Wenshan Hong a, Bolian Xu b,⇑
a
School of Chemistry and Chemical Engineering, Fuyang Normal College, Fuyang 236037, People’s Republic of China
b
Key Laboratory of Mesoscopic Chemistry of MOE, Jiangsu Provincial Key Laboratory of Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing University,
Nanjing 210093, People’s Republic of China

h i g h l i g h t s g r a p h i c a l a b s t r a c t
Under UV or visible light irradiation with energy (hv) greater than the band-gap energy of BiOI and/or
BiOI/ZnSn(OH)6 catalysts were ZnSn(OH)6, when ZnSn(OH)6 and BiOI were brought in contact, the energy levels difference between
prepared by a facile and economical ZnSn(OH)6 and BiOI caused that the electrons flowed from one phase to another. In this way, the photo-
route.19.7% BiOI/ZnSn(OH)6 showed generated electron–hole pairs BiOI/ZnSn(OH)6 composites were effectively separated.
the best photocatalytic activity.The
photocatalytic mechanism of BiOI/
ZnSn(OH)6 was discussed.A transfer
process of photogenerated carriers was
proposed. O +
2 and h were the main
reactive species for the degradation of
phenol.

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

Article history: BiOI/ZnSn(OH)6 composite photocatalysts with different weight percents of BiOI were successfully syn-
Received 8 December 2012 thesized by a facile and economical deposition method at 80 °C and characterized by X-ray diffraction
Received in revised form 21 May 2013 (XRD), high resolution transmission electron microscopy (HR-TEM), selected area electron diffraction
Accepted 22 May 2013
(SAED), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy, UV–vis diffuse
Available online 3 June 2013
reflection spectroscopy (UV–vis DRS) and Brunauer–Emmett–Teller (BET) surface area measurements.
Photocatalytic reforming of ethanol for H2 production and photocatalytic degradation of phenol over
Keywords:
BiOI/ZnSn(OH)6 samples were investigated. The results showed that the BiOI/ZnSn(OH)6 photocatalysts
Deposition method
H2 production
exhibited a coexistence of both tetragonal BiOI and cubic perovskite ZnSn(OH)6 phases. With increasing
ZnSn(OH)6 BiOI content, the absorption intensity of BiOI/ZnSn(OH)6 increased in the 280–550 nm region and the
BiOI absorption edge shifted significantly to longer wavelengths compared with that of pure ZnSn(OH)6.
Photocatalysis The 19.7% BiOI/ZnSn(OH)6 catalyst exhibited obviously higher photocatalytic activity as compared to
either pure ZnSn(OH)6 or BiOI, which could be primarily attributed to the presence of intimate contacts
between ZnSn(OH)6 and BiOI resulted in easier charge transfer and more efficient separation of electron–
hole pairs. The photocatalytic mechanism of BiOI/ZnSn(OH)6 was discussed.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction of photogenerated electron–hole pairs and the low conversion effi-

TiO2 has been a very attractive research topic for its outstanding
bulk and surface physicochemical properties as well as its potential
applications in solar energy conversion, photocatalytic hydrogen
evolution and photocatalytic degradation of environmental pollu-
tants [1–6]. However, TiO2 suffers from the high recombination
⇑ Corresponding authors. Tel.: +86 558 2596249; fax: +86 558 2596703.
E-mail addresses: cuiyumin0908@163.com (Y. Cui), xubolian@nju.edu.cn (B. Xu).
ciency of solar energy. The two main drawbacks of TiO2 limit its
industrial application. In order to overcome its drawbacks, one of
approaches is the modification of TiO2 with noble metals, such as
Pt [7], and Pd [8]. Nevertheless the stability of these modified
TiO2 has been concerned about owing to the oxidation of noble
metal nanoparticles on the TiO2 surface [9]. Furthermore, the
high cost of noble metal further hinders its application.
Therefore, the development of new efficient photocatalysts is still
in progress.

1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.05.086
 H. Li et al. / Chemical Engineering Journal 228 (2013) 1110–1120
In recent years, some new type semiconductor photocatalysts
such as a-Ga2O3 [10], Bi2WO6 [11–13], BiOCl [14], BiOBr [15], BiOI
[16], In(OH)3 [17,18], InOOH [19], ZnSn(OH)6 [20] and so on have
been developed. ZnSn(OH)6 has been widely used in high effective
flame retardants due to its nontoxicity and safety [21,22] and it is a
perovskite-structured hydroxide, and its surface is full of OH
groups which can accept photogenerated holes to form hydroxyl
radicals (OH), the principal reactive oxidant in photocatalytic reac-
tion [23]. In 2012, Chen et al. [20] reported that ZnSn(OH)6 had
high photocatalytic activity under UV light irradiation for the deg-
radation of benzene. In addition, Fu et al. [23] reported that
ZnSn(OH)6, even without the loading of noble metals, showed high
photocatalytic activity toward degradation of benzene and no
deactivation of the catalyst was observed under UV light irradia-
tion for 50 h. But ZnSn(OH)6 has a wide band-gap energy of
4.0 eV [20], therefore it can only use a small UV fraction of solar
light. In order to expand the optical response of ZnSn(OH)6 from
the UV to the visible light region and improve the separation effi-
ciency of photogenerated electron–hole pairs in the ZnSn(OH)6,
one of the common approaches is to combine it with narrow band
gap semiconductor.
Recently, BiOI (bismuth oxyiodide), as a promising photocata-
lyst, has drawn extensive interests of researchers owing to its po-
tential applications in the photocatalytic degradation of organic
pollutants [24–26]. BiOI has a small band-gap energy of 1.8 eV
and it has strong absorption in the visible light region. As a typical
p-type semiconductor, it may be a potential substitute for nobel
metal cocatalysts. In 2011, Jiang et al. [27] reported that the ZnO/
BiOI composite photocatalyst had higher photocatalytic activity
than pure ZnO and BiOI, and the enhanced photocatalytic activity
could be primarily attributed to the fact that the heterojunction
at the interface between BiOI and ZnO improved the separation
efficiency of photogenerated electron–hole pairs in the ZnO/BiOI
phtocatalyst. Thus, BiOI/ZnSn(OH)6 composites may be an ideal
system to expand the optical response to the visible light region
and improve the separation efficiency of photogenerated charge
carriers, and then achieve a high photocatalytic activity. Moreover,
to the best of our knowledge, there was no report on the prepara-
tion and photocatalytic performance in the BiOI/ZnSn(OH)6
system.
In this work, BiOI/ZnSn(OH)6 composite photocatalysts with dif-
ferent weight percents of BiOI were successfully synthesized by a
facile and economical deposition method at 80 °C, and the effect
of BiOI contents on the structure and photocatalytic activity of
BiOI/ZnSn(OH)6 catalysts was investigated in detail. Photocatalytic
reforming of ethanol for H2 production and photocatalytic degrada-
tion of phenol over BiOI/ZnSn(OH)6 samples were greatly enhanced
as compared to either pure ZnSn(OH)6 or BiOI. The photocatalytic
mechanism of BiOI/ZnSn(OH)6 was also investigated.
2. Experimental
2.1. Catalyst preparation
The ZnSn(OH)6 sample was prepared by a homogeneous precip-
itation method. In a common preparation, equal volume of
0.6 mol L1 NaOH and 0.1 mol L1 ZnCl2 aqueous solution was
added into subsequently 0.1 mol L1 SnCl4 solution with magnetic
stirring at room temperature. The above mixed aqueous solution
was stirred for 40 min to obtain a slurry. Then the slurry was
washed repeatedly with deionized water and separated by filtra-
tion. The product was finally dried at 80 °C in air.
The BiOI/ZnSn(OH)6 samples with different BiOI contents were
prepared by a deposition method. In a typical experiment, different
stoichiometric amounts of Bi(NO3)35H2O and 0.05 g KI were
1111
dissolved in 20 mL ethylene glycol to obtain a clear solution I.
ZnSn(OH)6 (1.0 g) was ultrasonically dispersed into deionized
water to form a homogeneous mixture II. Then the solution I was
added dropwise into the mixture II under strong stirring. After
being stirred for 1.0 h at room temperature, the resulting mixtures
were heated at 80 °C for 2.0 h in a water bath. Finally, the precip-
itates were collected, washed thoroughly with deionized water
and ethanol, and dried at 50 °C in air. The final samples with
weight percents of BiOI of 11.0, 19.7 and 32.9 wt%, were denoted
as 11.0%, 19.7% and 32.9% BiOI/ZnSn(OH)6, respectively. For com-
parison, pure BiOI powder was prepared by adopting the method
mentioned above in the absence of ZnSn(OH)6, and the synthesis
process of pure BiOI was referred to the literature [27].
2.2. Catalyst characterization
X-ray diffraction (XRD) were performed on a Philips X’ pert dif-
fractometer equipped with Ni-filtered Cu Ka radiation source
(k = 0.15418 nm). X-ray photoelectron spectra (XPS) measurements
were carried out using Multilab 2000 XPS system with a monochro-
matic Mg Ka source and a charge neutralizer (Multilab 2000 XPS,
Thermo Scientific, America). The Brunauer–Emmett–Teller (BET)
surface areas of samples were determined from N2 adsorption iso-
therms at 77 K using a Micromeritics ASAP 2020 instrument with a
computer-controlled measurement system. High resolution trans-
mission electron microscopy (HR-TEM) images and selected area
electron diffraction (SAED) were taken using a JEM-2100 electron
microscope. UV–vis diffuse reflection spectroscopy (UV–vis DRS)
of the samples was determined with a Shimadzu UV-3600 spectro-
photometer (Japan) using BaSO4 as a reference. The photolumines-
cence (PL) spectroscopy, obtained at room temperature with an
excitation wavelength of 280 nm, were recorded on a CARY Eclipse
(America) fluorescence spectrophotometer.
2.3. Photocatalytic reaction
2.3.1. Photocatalytic reforming of ethanol to H2
Photocatalytic reforming of ethanol for H2 production reactions
was performed under N2 (>99.99%) atmosphere in a top-irradiation
quartz reaction cell (18-cm-long, 7-cm-diameter), which was con-
nected to a closed gas-recirculation tube system. In a typical exper-
iment, BiOI/ZnSn(OH)6 photocatalysts (0.05 g) were first suspended
in 170 mL ethanol aqueous solution (containing 5.0 mL ethanol).
After stirring for 40 min, the suspension was illuminated by a
high-pressure mercury lamp (kmax = 254 nm, 125 W) during UV
light experiments or by a 400 W metal halide lamp (kmax = 588 nm)
with the combination of a cut-off filter (k > 400 nm) to eliminate UV
radiation during visible light experiments. The solution tempera-
ture was maintained at about 30 °C by circulating water through
a jacket around the reactor. The generated gas of H2 was deter-
mined by an online gas chromatograph (GC, model DS 6200; Donam
Instruments Inc., Gyeonngi-do, Korea).
2.3.2. Photocatalytic degradation of phenol
Photoacatalytic degradation of phenol was performed in an
aqueous solution. The UV light was obtained by four 4 W fluores-
cent UV bulbs (TUV 4 W/G4 T5, Philips, kmax = 254 nm). The visible
light source was a 400 W metal halide lamp (kmax = 588 nm) with
the combination of a cut-off filter (k > 400 nm) to eliminate UV
radiation during visible light experiments. For each UV light test,
150 mL phenol aqueous solution (2.12  104 mol L1) and 0.08 g
catalyst samples were used in an internal-irradiation quartz reac-
tion cell (250 mL), while for each visible light test, 40 mL phenol
aqueous solution (1.06  104 mol L1) and 0.05 g catalyst samples
were used in an internal-irradiation quartz reaction cell (50 mL). A
general procedure was carried out as follows. First, phenol aqueous
1112 H. Li et al. / Chemical Engineering Journal 228 (2013) 1110–1120

solution was placed into a water-jacketed reactor maintained at Table 1

25 °C, and then the catalyst samples were suspended in the solu- Atomic composition, average crystallite size (L) and BET surface areas (SBET) of BiOI,
ZnSn(OH)6, 11.0%, 19.7% and 32.9% BiOI/ZnSn(OH)6 samples.
tion. The suspension was stirred vigorously for 1.0 h in the dark
to establish the adsorption–desorption equilibrium of phenol, then Sample Elements (atomic L (nm) SBET (m2 g1)
irradiated under UV or visible light. About 2.5 mL solution was composition %)

withdrawn from the reactor periodically and centrifuged and ana- Zn Sn O Bi I

lyzed for the degradation of phenol by using a TU-1901 ZnSn(OH)6 5.1 7.4 42.7 – – 46.5 25.7
spectrophotometer. 11.0% BiOI/ZnSn(OH)6 4.2 6.1 38.9 3.8 2.2 43.7 34.2
In order to investigate the effect of relevant reactive species, a 19.7% BiOI/ZnSn(OH)6 3.4 5.0 37.2 6.4 5.6 41.4 37.8
32.9% BiOI/ZnSn(OH)6 2.9 3.1 35.2 8.3 7.1 38.3 40.4
quantity of different appropriate species quenchers were intro-
BiOI – – 20.8 18.5 16.1 34.8 23.4
duced into the photocatalytic degradation process of phenol in a
manner similar to the photodegradation experiment. The dosages
of these species quenchers were referred to the literatures [28,29].

2.4. Reuse of photocatalyst

The 19.7% BiOI/ZnSn(OH)6 photocatalyst was immersed in eth-

anol for 5.0 h and rinsed with deionized water, and then dried at
80 °C. After this, the 19.7% BiOI/ZnSn(OH)6 photocatalyst was re-
used for the degradation of phenol, and the reuse experiment
was done for five times.

3. Results and discussion

3.1. Catalyst structure

Fig. 1 shows the XRD patterns of BiOI/ZnSn(OH)6 samples with

different BiOI contents. It can be seen that 19.7% and 32.9% BiOI/
ZnSn(OH)6 samples exhibit a coexistence of both tetragonal BiOI
(JCPDS card No. 73-2062) and cubic perovskite ZnSn(OH)6 (JCPDS
card No. 20-1455) phases, the peaks around 2h of 29.7°, 31.7°,
and 45.6° were indexed to those of tetragonal BiOI and correspond
to (0 1 2), (1 1 0), and (0 2 0), respectively. When the amount of BiOI
is lower than 19.7%, no significant diffraction peak of BiOI can be
detected, which can be ascribed to its lower content and high dis-
persion on the surface of ZnSn(OH)6 particles. The average crystal-
lite sizes of ZnSn(OH)6 in the BiOI/ZnSn(OH)6 composites were
calculated from the (200) peaks, according to the Scherrer formula
[30]: L = 0.90k/bcos h, and the results were listed in Table 1.
Fig. 2 exhibits the XRD patterns of the 19.7% BiOI/ZnSn(OH)6
catalyst before and after 5.0 h irradiation of UV and visible light
for the degradation of phenol. It can be clearly observed that the
phase and structure of the 19.7% BiOI/ZnSn(OH)6 catalyst remained
unchanged after reaction, which suggests that the catalyst is stable
in the photocatalytic degradation process of phenol.
Based on the nitrogen adsorption–desorption isotherms, the
BET surface areas of ZnSn(OH)6, BiOI, 11.0%, 19.7% and 32.9%
Fig. 1. XRD patterns of BiOI/ZnSn(OH)6 samples with different BiOI contents (wt%):
(a) 0.00, (b) 11.0, (c) 19.7, (d) 32.9 and (e) 100.
Fig. 2. XRD patterns of the 19.7% BiOI/ZnSn(OH)6 catalyst before and after 5.0 h UV
and visible light irradiation.
BiOI/ZnSn(OH)6 samples were calculated and summarized in Ta-
ble 1, respectively. It can be seen that the BET surface areas of
BiOI/ZnSn(OH)6 composites are obviously higher than those of
pure BiOI and ZnSn(OH)6. In general, a greater BET surface area
of photocatalysts can supply more surface active sites, leading to
an enhancement of the photocatalytic performance [31]. However,
the corresponding BET surface areas of 11.0%, 19.7% and 32.9%
BiOI/ZnSn(OH)6 samples did not have obvious difference in Table 1,
which demonstrates that the BET surface area is not the main influ-
encing factor for the photocatalytic performance of different BiOI/
ZnSn(OH)6 samples.
The chemical composition and surface chemical states of the
BiOI/ZnSn(OH)6 samples were further investigated by X-ray photo-
electron spectroscopy (XPS). The peak positions in all of the XPS
spectra were calibrated with C 1s at 284.6 eV. The typical survey
XPS spectrum of the 19.7% BiOI/ZnSn(OH)6 sample indicates that
the catalyst consists of Sn, Zn, Bi, O and I elements (Fig. 3A). As dis-
played in Fig. 3B and C, the binding energy of Bi 4f and I 3d of 19.7%
BiOI/ZnSn(OH)6 shifts to the higher values compared with that of
Bi 4f and I 3d of pure BiOI at 158.4 eV (Bi 4f7/2) and 163.7 eV (Bi
4f5/2) [26,32], 618.1 eV (I 3d5/2) and 629.6 eV (I 3d3/2) [26], respec-
tively. In Fig. 3D, the binding energy of Zn 2p3/2 of 19.7% BiOI/
ZnSn(OH)6 also shifts to a higher value compared with that of Zn
2p3/2 of pure ZnSn(OH)6 at 1022.0 eV [33]. Above results probably
suggest that there is a strong interaction between BiOI and
ZnSn(OH)6 nanoparticles. The photoelectron peaks at 495.0 and
486.6 eV of ZnSn(OH)6 and 19.7% BiOI/ZnSn(OH)6 samples shown
in Fig. 2E correspond to the binding energies of Sn 3d3/2 and Sn
3d5/2, respectively, which is in accordance with those in the litera-
ture [34]. Because the combination with Bi or I cannot cause obvi-
ous change in the binding energy of Sn 3d, it was hard to say
whether there were chemical bonds existing between Bi or I and
Sn simply, but Bi or I may have a strong interaction with other ele-
ments except Sn in BiOI/ZnSn(OH)6 from XPS characterization [35].
 H. Li et al. / Chemical Engineering Journal 228 (2013) 1110–1120 1113

Fig. 3. XPS survey spectra of the 19.7% BiOI/ZnSn(OH)6 sample (A) and XPS spectra Bi 4f (B), I 3d (C), Zn 2p (D) and Sn 3d (E) of different samples.

The above XPS analysis results at least confirmed that BiOI/
ZnSn(OH)6 was indeed a composite of BiOI and ZnSn(OH)6. The
XPS results further confirm the coexistence of ZnSn(OH)6 and BiOI
in the BiOI/ZnSn(OH)6 samples. The atomic composition of BiOI,
ZnSn(OH)6, 11.0%, 19.7% and 32.9% BiOI/ZnSn(OH)6 samples was
also analyzed by X-ray photoelectron spectroscopy (XPS) study,
and the results were listed in Table 1. In 11.0% BiOI/ZnSn(OH)6
sample, BiOI nanoparticles are detected on the ZnSn(OH)6 surface
and atomic concentration of Bi and I are only 3.8% and 2.2%. With
the increase of the loaded BiOI contents, atomic concentration of Bi
and I increases to 18.5% and 16.1% in 32.9% BiOI/ZnSn(OH)6, and
there is a similar trend between at% from XPS and the nominal
BiOI%, which implies that the ZnSn(OH)6 may be covered by BiOI
nanoparticles [36,37].
Fig. 4A presents the HR-TEM image of the 19.7% BiOI/ZnSn(OH)6
sample in which we can observe different lattice fringes. The HR-
TEM image reveals the highly crystalline nature of the sample.
Clear fringe with an interval of 0.302 nm could be indexed to
(0 1 2) lattice plane of tetragonal BiOI and that of 0.385 nm agreed
with the (2 0 0) lattice plane of cubic perovskite ZnSn(OH)6, which
demonstrated that the heterojunction might be formed between
BiOI and ZnSn(OH)6. The results were consistent with what we ob-
tained from the XRD patterns in Fig. 1.
As shown in the corresponding SAED pattern (Fig. 4B), diffrac-
tion spots with d values of 0.388 and 0.303 nm are observed, which
correspond to the (2 0 0) lattice plane of cubic perovskite
ZnSn(OH)6 and (0 1 2) lattice plane of tetragonal BiOI, respectively.
This can also be regarded as a proof for the coexistence of BiOI and
ZnSn(OH)6.
The optical properties of the BiOI/ZnSn(OH)6 samples with dif-
ferent BiOI contents were investigated by UV–vis diffuse reflec-
tances spectroscopy. As revealed from Fig. 5A, with increasing
1114 H. Li et al. / Chemical Engineering Journal 228 (2013) 1110–1120

Fig. 4. HR-TEM image (A) and SAED pattern (B) of the 19.7% BiOI/ZnSn(OH)6 sample.

Fig. 5. UV–vis diffuse reflectances spectra (A) of BiOI/ZnSn(OH)6 samples with different BiOI contents (wt%): (a) 0.00, (b) 11.0, (c) 19.7, (d) 32.9 and (e) 100, and the plotting of
(ahv)1/2 versus photon energy (B) and the plotting of (ahv)2 versus photon energy (C).

BiOI contents, the absorption intensity of BiOI/ZnSn(OH)6 samples
increased in the 280–550 nm light region and the absorption edge
shifted significantly to longer wavelengths as compared to pure
ZnSn(OH)6 sample, clearly revealing that the absorption edges of
BiOI/ZnSn(OH)6 samples shifted to the lower energy region. It is
well known that the optical absorption near the band edge of a
crystalline semiconductor follows the formula: ahv = A(hv  Eg)n/
2
, where a, A, v and Eg are the absorption coefficient, a constant,
light frequency and band-gap energy, respectively [38]. Among
them, n depends on the characteristics of the transition in a semi-
conductor (direct transition: n = 1; indirect transition: n = 4). For
pure BiOI, the value of n is 4 [39], and for pure ZnSn(OH)6, the value
of n is 1 [40]. The band-gap energy (Eg value) of pure BiOI sample
can be thus estimated from a plot of (ahv)1/2 versus photon energy
(hv), as shown in Fig. 5B, and the band-gap energy (Eg value) of
pure ZnSn(OH)6 sample can be thus estimated from a plot of
(ahv)2 versus photon energy (hv), as shown in Fig. 5C. The intercept
of the tangent to the x-axis will give a good approximation of the
band-gap energies for the pure BiOI and ZnSn(OH)6 samples,
repectively.
The valence band (VB) edge position and the conduction band
(CB) edge position of BiOI and ZnSn(OH)6 at the point of zero charge
were calculated by the following empirical formulas [32,39]:
EVB ¼ X  Ee þ 0:5Eg ð1Þ
ECB ¼ EVB  Eg ð2Þ
where EVB was the valence band (VB) potential, and ECB was the
conduction band (CB) potential. X was the electronegativity of the
 H. Li et al. / Chemical Engineering Journal 228 (2013) 1110–1120
semiconductor, and Ee was the energy of free electrons on the
hydrogen scale (4.5 eV). Eg was the band-gap energy of the semi-
conductor and it was shown in Fig. 5B and C. Accordingly, the EVB of
BiOI and ZnSn(OH)6 were estimated to be 2.31 and 4.20 eV, respec-
tively. The ECB of BiOI and ZnSn(OH)6 were 0.57 and 0.49 eV,
respectively.
3.2. Adsorption studies
It is well known that the activity of photocatalyst is related to
its adsorbability [41,42]. Therefore, a research of phenol adsorption
was performed on BiOI, ZnSn(OH)6, 11.0%, 19.7% and 32.9% BiOI/
ZnSn(OH)6 photocatalysts by using 15 mg of photocatalyst at room
temperature in the dark. The adsorption capacity of all samples
was presented in Fig. 6, in which the adsorption behaviors of phe-
nol on all samples followed the Langmuir model. It can be seen that
phenol uptake capacity moderately increases in the presence of the
11.0%, 19.7% and 32.9% BiOI/ZnSn(OH)6 photocatalyst compared
with that of the pure ZnSn(OH)6 or BiOI photocatalyst. The ad-
sorbed quantities of phenol, qt (mg g1 catalyst ), at time t were calcu-
lated according to Eq. (3):
qt ¼ ½ðC 0  C t Þ  1000  MW  V 0 =wcatalyst
where C0 and Ct (mol L1) were the initial concentrations and con-
centration at time t of phenol, respectively; MW was the molecular
weight of phenol (g mol1); V0 was the volume of phenol aqueous
solution (L); and wcatalyst was the mass of photocatalyst (g). The
Fig. 6. Phenol adsorptivity plot for BiOI/ZnSn(OH)6 samples with different BiOI
contents (wt%): (a) 0.00, (b) 11.0, (c) 19.7, (d) 32.9 and (e) 100.
Fig. 7. Effects of BiOI content (wt%) in the BiOI/ZnSn(OH)6 catalysts on the degradation of phenol under UV (A) (kmax = 254 nm) and visible (B) (kmax = 588 nm) light
irradiation: (a) 0.00, (b) 11.0, (c) 19.7, (c’) 19.6, (d) 32.9 and (e) 100 (Deposition method (a–e), Mechanically mixed (c0 )).
1115
equilibrium adsorption capacity (qe) was usually estimated by the
pseudo-first-order and pseudo-second-order model, and the correct
values were chosen according to the higher correlation coefficient
R2 [43,44]. Herein, the equilibrium adsorption capacity (qe) of BiOI,
ZnSn(OH)6 and 11.0%, 19.7%, 32.9% BiOI/ZnSn(OH)6 catalysts is 7.43,
7.86, 10.02, 10.75 and 11:27 mg g1catalyst , respectively. Obviously, the
adsorption ability of the ZnSn(OH)6 was enhanced by introduction
of BiOI, which is a prequisite for good photocatalytic activity [45],
but the absorbance ability of 11.0%, 19.7% and 32.9% BiOI/
ZnSn(OH)6 samples did not have obvious difference, demonstrating
that the absorbance ability was also not the main influencing factor
for the photocatalytic activities of different BiOI/ZnSn(OH)6
samples.
3.3. Photocatalytic activity
3.3.1. Photocatalytic degradation of phenol
The effect of BiOI contents on the photocatalytic activity of BiOI/
ZnSn(OH)6 photocatalysts has been investigated by phenol degra-
dation in an aqueous solution under UV and visible light irradiation
(Fig. 7). It can be seen that under UV and visible light irradiation
ð3Þ the self-degradation of phenol is negligible in the absence of pho-
tocatalyst, indicating that the photolysis can be ignored. While in
the presence of photocatalysts, the irradiation of UV and visible
light can result in the obvious degradation of phenol, and the BiOI
content in the ZnSn(OH)6 exerts great influences on the photocat-
alytic activity of BiOI/ZnSn(OH)6 photocatalysts. With BiOI content
increasing, the photocatalytic activities of BiOI/ZnSn(OH)6 photo-
catalysts under UV and visible light irradiation first increase,
reaching the maximums at BiOI content of 19.7%, respectively,
and then decrease with further increasing BiOI content. A similar
effect of BiOI content on photocatalytic activity was also reported
in the BiOI/BiOBr [39] and BiOI/Bi2WO6 [45] systems.
In generally, the photocatalytic activity of composite photocat-
alyst is related to its BET surface areas, absorbance abilities, com-
ponent contents, band structure matching and heterojunction
interface, etc. But the corresponding BET surface areas (Table 1)
and the absorbance abilities (Fig. 6) of 11.0%, 19.7%, 32.9% BiOI/
ZnSn(OH)6 samples did not have obvious difference, which demon-
strates that the main influencing factor for the enhanced photocat-
alytic performance of BiOI/ZnSn(OH)6 samples is more likely to be
the heterojunction structure rather than both BET surface areas
and absorbance abilities. With the increase of BiOI content in
BiOI/ZnSn(OH)6 from 11.0% to 19.7%, the more contact areas be-
tween BiOI and ZnSn(OH)6 will be formed, which facilitates the
efficient separation of photoinduced electrons and holes, leading
1116 H. Li et al. / Chemical Engineering Journal 228 (2013) 1110–1120

to the enhanced photocatalytic performance. However, If the con-
tent of BiOI increases continuously to excess, more BiOI and BiOI
contacts were established, which dominated the BiOI and
ZnSn(OH)6 contacts. Since BiOI and BiOI contacts were not as effec-
tive as BiOI and ZnSn(OH)6 contacts for an effective charge separa-
tion. Moreover, the excessive BiOI with narrow band gap could be
acted as the recombination center of electrons and holes [39],
impeding the photocatalytic activity on the contrary. Thus, 19.7%
BiOI/ZnSn(OH)6 with an appropriate BiOI content exhibited the
highest photocatalytic activity.
In order to confirm the advantage of intimate contacts between
BiOI and ZnSn(OH)6, 19.7% BiOI/ZnSn(OH)6 was compared with the
mechanical mixture of BiOI and ZnSn(OH)6 with the similar com-
position under identical photocatalytic degradation conditions, as
shown in Fig. 7. Obviously, the UV and visible light photocatalytic
activity of mechanically mixed 19.6% BiOI/ZnSn(OH)6 were lower
than that of 19.7% BiOI/ZnSn(OH)6 prepared by deposition method.
This was mainly because BiOI and ZnSn(OH)6 behaved as indepen-
dent photocatalysts rather than a coupled system in the mechani-
cal mixture of BiOI and ZnSn(OH)6, which was unfavorable to the
transfer of charge carriers from one phase to another. However,
the photocatalytic activity of mechanical mixture of BiOI and
ZnSn(OH)6 was enhanced compared with that of pure BiOI and
ZnSn(OH)6, even the mathematical sum of them. This might be ow-
ing to the inevitable partial contact between BiOI and ZnSn(OH)6 in
the mechanical mixture of BiOI and ZnSn(OH)6, which was in favor
of the photocatalytic activity to some extent but was still far infe-
rior to the effect of BiOI/ZnSn(OH)6 composites. The results showed
that that there were strong interactions between different phases
in the BiOI/ZnSn(OH)6 prepared by deposition method.
The photocatalytic degradation of organic pollutants ususally
follows first-order kinetics [46]. The linear relationship between
ln(C0/C) and t shown in Fig. 8 confirmed that the photocatalytic
degradation process of phenol followed the apparent pseudo-
first-order model expressed as Eq. (4) [47–49]:
t
lnðC 0 =CÞ ¼ kapp ð4Þ
where kapp was the apparent pseudo-first-order rate constant
(min1), C was phenol concentration in aqueous solution at time t
(mol L1), C0 was initial phenol concentration (mol L1). Thus, the
kapp of as-prepared samples were calculated and shown in Fig. 9,
respectively. It can be seen that the kapp for phenol photodegrada-
tion over the 19.7% BiOI/ZnSn(OH)6 catalyst under UV and visible
light irradiation was about 3.7 and 13.5 times, 7.9 and 2.8 times
higher than that over pure ZnSn(OH)6 and BiOI, respectively. Other
BiOI/ZnSn(OH)6 catalysts also has much higher kapp values than
pure ZnSn(OH)6 and BiOI, but lower than 19.7% BiOI/ZnSn(OH)6
photocatalyst. The result suggests that BiOI/ZnSn(OH)6 displayed
the enhanced photocatalytic activities than the single ZnSn(OH)6
and BiOI while 19.7% BiOI/ZnSn(OH)6 had the best photocatalytic
activity compared to 11.0% BiOI/ZnSn(OH)6 and 32.9% BiOI/
ZnSn(OH)6.
To test the stability of the 19.7% BiOI/ZnSn(OH)6 sample for the
photocatalytic reaction of phenol under UV and visible light irradi-
ation, the catalyst was reused for photocatalytic reaction 5 times

Fig. 8. Linear transform ln(C0/C) = f(t) of the kinetic curves of phenol degradation over BiOI/ZnSn(OH)6 catalysts with different BiOI contents (wt%) under UV (A)
(kmax = 254 nm) and visible (B) (kmax = 588 nm) light irradiation: (a) 0.00, (b) 11.0, (c)19.7, (c0 ) 19.6, (d) 32.9 and (e)100 (Deposition method (a–e), Mechanically mixed (c0 )).

Fig. 9. Photocatalytic degradation rate constant k of phenol as a function of BiOI content (wt%) under UV (A) (kmax = 254 nm) and visible (B) (kmax = 588 nm) light irradiation:
(a) 0.00, (b) 11.0, (c) 19.7, (c0 ) 19.6, (d) 32.9 and (e) 100 (Deposition method (a–e), Mechanically mixed (c0 )).
 H. Li et al. / Chemical Engineering Journal 228 (2013) 1110–1120 1117

Fig. 10. Reuse in the photocatalytic degradation of phenol in the presence of 19.7% BiOI/ZnSn(OH)6 catalyst under UV (A) (kmax = 254 nm) and visible (B) (kmax = 588 nm) light
irradiation.

Fig. 11. The amounts of H2 generated (A and B) and the H2 evolution rate obtained (C and D) over BiOI/ZnSn(OH)6 catalysts with different BiOI contents (wt%) under UV (A, C)
and visible (B, D) light irradiation: (a) 0.00, (b) 11.0, (c) 19.7, (d) 32.9 and (e) 100.

under the same conditions and the result is shown in Fig. 10. It can
be seen that the photocatalytic activity does not exhibit any signif-
icant loss after five recycles for the photodegradation of phenol,
which indicate that the catalyst is stable for the photocatalysis of
phenol molecules.
3.3.2. Photocatalytic reforming of ethanol to H2
The effect of BiOI contents on the photocatalytic reforming of
ethanol to H2 over BiOI/ZnSn(OH)6 photocatalysts under UV and
visible light irradiation was also investigated. Blank experiments
showed that without photocatalysts or irradiation, no H2 was pro-
duced. The amounts of H2 produced over BiOI/ZnSn(OH)6 photocat-
alysts under UV and visible light irradiation were plotted as a
function of time in Fig. 11A and B, respectively. It can be seen that
the generation of H2 almost linearly increases with irradiation
time. The corresponding H2 evolution rates were showed in
Fig. 11C and D, respectively. Clearly, pure BiOI shows very poor
activity for hydrogen generation under UV light irradiation
(Fig. 11C), which is mainly because pure BiOI with narrow band
gap could be easily acted as the recombination center of electrons
and holes. Fig. 11D shows that the ZnSn(OH)6 alone has no photo-
catalytic activity for H2 production under visible light irradiation,
which can be attributed to the fact that pure ZnSn(OH)6 with a
large band-gap energy (3.71 eV) cannot be excited by visible light.
1118 H. Li et al. / Chemical Engineering Journal 228 (2013) 1110–1120
The photocatalytic activities of BiOI/ZnSn(OH)6 composite photo-
catalysts under UV and visible light irradiation first increase with
the increment of BiOI component, reaching a maximum at BiOI
content of 19.7%, whereas a further increase in the amount of BiOI
component leads to a decrease in H2 evolution rates.
The enhanced photocatalytic activities of BiOI/ZnSn(OH)6 com-
posites are attributed to the synergic effect between BiOI and
ZnSn(OH)6, which plays a key role to the effective separation of
photogenerated electron–hole pairs. At lower BiOI content, a good
dispersion of BiOI on the ZnSn(OH)6 surface could be achieved,
which is supported by the XRD analysis (Fig. 1). In this case,
the increase of BiOI content would lead to more BiOI generated
on the ZnSn(OH)6 surface, which creates larger BiOI-ZnSn(OH)6
contact areas and allows more efficient charge transfer between
ZnSn(OH)6 and BiOI. However, excess BiOI loading, the fine BiOI
nanoparticles might be agglomerated, leading to a relatively poor
dispersion, and the excessive BiOI with narrow band gap could be
also acted as the recombination center of electrons and holes
[39], which is unfavorable for high photocatalytic efficiency of
the BiOI/ZnSn(OH)6, as a result, the hydrogen generation gradu-
ally becomes worse. Therefore, there is an optimal loading of
19.7% BiOI on ZnSn(OH)6, which showed the best photocatalytic
activity in our studies.
3.4. Photocatalytic mechanism
3.4.1. Effects of reactive species
The effect of various radical scavengers on the degradation of
phenol over the 19.7% BiOI/ZnSn(OH)6 sample under UV and visi-
ble light irradiation was performed to study the underlying photo-
degradation mechanism. Benzoquinone (BQ), as an  O 2 scavenger,
was introduced to the reaction system [28,50]. As the scavenger
of  OH, isopropanol (IPA), was added to the reaction system
[28,51]. In order to investigate the role of h+ and H2O2 radical spe-
cies, ammonium oxalate (AO) [29] and catalase (CAT) [28] were
also introduced to the reaction system, respectively. The results
were shown in Fig. 12. Once the radical species played a major role
in the degradation of phenol, the degradation ratio was expected to
be decreased remarkablely.
As shown in Fig. 12, the addition of IPA had a negligible effect on
the degradation ratio of phenol compared with no scavenger under
otherwise identical conditions, indicating that  OH was not the
main reactive species. However, the degradation ratio of phenol
decreased significantly after the addition of BQ, AO and CAT,
respectively. That is to say,  O + +
2 , h and H2O2, especially h and
 
O2 , jointly dominated the photodegradation process of phenol
while  OH could be ignored.
Fig. 12. The effect of different scavengers on the degradation of phenol over the 19.7% BiOI/ZnSn(OH)6 sample under UV (A) and visible (B) light irradiation.
3.4.2. Photocatalytic activity enhancement mechanism of BiOI/
ZnSn(OH)6
On the basis of the above experimental studies, a schematic dia-
gram of the band levels of the BiOI/ZnSn(OH)6 composites and the
possible reaction mechanism of the photocatalytic procedure are
proposed and illustrated in Fig. 13. It is well known that using
two semiconductors in contact with different redox energy levels
of conduction band (CB) and valence band (VB) can be used to im-
prove photogenerated carriers separation and enhance the effi-
ciency of the interfacial charge transfer [27]. The relative
positions of energy bands of ZnSn(OH) (EVB = 4.20 eV, ECB = 0.49 -
eV) and BiOI (EVB = 2.31 eV, ECB = 0.57 eV) are known and shown
in Fig. 13. It can be seen that both ZnSn(OH)6 and BiOI can be
simultaneously excited to form electron–hole pairs under UV light
irradiation, then the photoinduced electrons can transfer easily
from the CB bottom of ZnSn(OH)6 to that of BiOI. When ZnSn(OH)6
and BiOI semiconductors are in contact, the conduction band (CB)
potential of ZnSn(OH)6 is more negative than that of BiOI. There is
hence diffusion of electrons from ZnSn(OH)6 to BiOI, resulting in
accumulation of negative charges in BiOI close to the junction. At
the same time, the holes transfer from BiOI to ZnSn(OH)6, leaving
a positive section in ZnSn(OH)6 near the junction. With equilibra-
tion of BiOI and ZnSn(OH)6 Fermi levels, an internal electric field
directed from ZnSn(OH)6 to BiOI is simultaneously built to stop
the charge diffusion from ZnSn(OH)6 into BiOI. Meanwhile, the en-
ergy bands of ZnSn(OH)6 shifted downward along with the Fermi
level, whereas the energy bands of BiOI shift upward in this pro-
cess [27,32,39,52–54] (Fig. 13B). Under the irradiation of visible
light, BiOI is excited and there is the generation of electron–hole
pairs. This new CB edge potential (about 0.65 eV) [32,39,52] of
BiOI is more negative than that of ZnSn(OH)6, resulting in the pho-
toinduced electrons at the surface of BiOI can easily migrate to the
CB energy level of ZnSn(OH)6, while the excited holes remain on
the VB of BiOI. Furthermore, the migration of photogenerated elec-
trons and holes can be promoted by the internal electric field. Thus,
the recombination of photogenerated electron–hole pairs could be
effectively inhibited and the corresponding UV and visible light
photocatalytic activities would be greatly improved, as clarified
by following equations:
þ
BiOI þ hv ðUV or visibleÞ ! ecb þ hvb ð5Þ
þ
ZnSnðOHÞ6 þ hv ðUVÞ ! ecb þ hvb ð6Þ
ecb þ O2 !  O2 ð7Þ
ecb þ  O2 þ 2Hþ ! H2 O2 ð8Þ
 H. Li et al. / Chemical Engineering Journal 228 (2013) 1110–1120
Fig. 13. Diagrams of energy position and photogenerated electron–hole pairs transfer of BiOI and ZnSn(OH)6 under UV (A) and visible (B) light irradiation.
2ecb þ 2Hþ ! H2 ð9Þ
phenol þ  O2 ! products ð10Þ
phenol þ H2 O2 ! products ð11Þ
þ
phenol þ hvb ! products ð12Þ
When irradiation with energy (hv) greater than the band-gap en-
þ
ergy of BiOI and ZnSn(OH)6, electron–hole pairs (ecb  =hvb ) are gen-
þ
erated in BiOI and ZnSn(OH)6 (Eqs. (5) and (6)). Then, the (ecb  =hvb
pairs migrated to the surface of the catalysts and reacted with the
species adsorbed on the surface (e.g. Eqs. (7)–(12)). These reactions
þ
prevented the e cb =hvb pairs from combining. The better separation
of electrons and holes in the BiOI/ZnSn(OH)6 photocatalysts was
confirmed by photoluminescence (PL) emission spectra of pure
ZnSn(OH)6 and 19.7% BiOI/ZnSn(OH)6 photocatalysts in Fig. 14.
It is well known that PL emission spectra have been a useful
technique to investigate the separation efficiency of photogenerat-
ed charge carriers in a semiconductor photocatalyst [55–59]. The
comparison of PL emission spectra (excited at 280 nm) of pure
ZnSn(OH)6 and 19.7% BiOI/ZnSn(OH)6 photocatalysts at room tem-
perature was shown in Fig. 14. It can be seen that pure ZnSn(OH)6
and 19.7% BiOI/ZnSn(OH)6 photocatalysts have a broad emission
peak in the wavelength range of 370–430 nm. The strongest emit-
ting peaks around 385 nm are similar while PL emission intensity
of the 19.7% BiOI/ZnSn(OH)6 photocatalyst is dramatically weak-
ened compared with that of pure ZnSn(OH)6 photocatalyst, indicat-
ing that the recombination of photogenerated charge carriers was
Fig. 14. Photoluminescence (PL) spectra of ZnSn(OH)6 and 19.7% BiOI/ZnSn(OH)6
samples recorded at room temperature with the excitation wavelength of 280 nm.
1119
greatly inhibited by the BiOI introduction. In other words, an
appropriate amount of BiOI in the ZnSn(OH)6 was helpful to sepa-
rate the photogenerated charge carriers and increase the lifetime of
charge carriers, and then improve the photocatalytic perfomance
of BiOI/ZnSn(OH)6 photocatalysts.
4. Conclusions
In summary, the BiOI/ZnSn(OH)6 composite photocatalysts with
different BiOI contents were successfully synthesized by a facile
and economical deposition method at 80 °C. With increasing BiOI
content, the absorption intensity of BiOI/ZnSn(OH)6 samples in-
creased in the 280–550 nm light region and the absorption edge
shifted significantly to longer wavelengths as compared to pure
ZnSn(OH)6 sample. Photocatalytic reforming of ethanol for H2 pro-
duction and photocatalytic degradation of phenol over the 19.7%
BiOI/ZnSn(OH)6 sample were greatly enhanced as compared to
either pure ZnSn(OH)6 or BiOI sample, which could be primarily
attributed to the presence of intimate contacts between ZnSn(OH)6
and BiOI resulted in easier charge transfer and more efficient sep-
aration of electron–hole pairs. The tests of radical scavengers con-
firmed that  O +
and H2O2, especially h+ and  O
2, h 2 , jointly
dominated the photodegradation process of phenol while  OH
could be ignored. This work provides a simple and economical
route to couple two different semiconductors with different phys-
icochemical properties for developing novel high-performance
photocatalysts.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China (21201037) and Natural Science Foundation of
Higher Education Institutions in Anhui Province (KJ2012A217)
and Anhui Provincical Key Laboratory for Degradation and Moni-
toring of Pollution of the Environment.
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