Applied Surface Science 396 (2017) 492–496

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Applied Surface Science

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Full length article

Facile synthesis of hierarchical double-shell WO3 microspheres with

enhanced photocatalytic activity
Zhenfeng Wang a,c , Deqing Chu a,c,∗ , Limin Wang b,c,∗∗ , Lipeng Wang b , Wenhui Hu a ,
Xiangyu Chen a , Huifang Yang a , Jingjing Sun b
a
College of Environment and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, PR China
b
School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, PR China
c
State Key Laboratory of Hollow-Fiber Membrane Materials and Membrane Processes, Tianjin 300387, PR China

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

Article history: Hierarchical double-shell WO3 microspheres (HDS-WO3 ) have been successfully obtained through the
Received 3 June 2016 thermal decomposition of WO3 ·H2 O formed by metal salts as the templates. The products were character-
Received in revised form 3 October 2016 ized by X-ray diffraction (XRD), and the morphology was investigated by scanning electron microscopy
Accepted 27 October 2016
(SEM) and transmission electron microscopy (TEM). In addition, the HDS-WO3 microspheres were
Available online 31 October 2016
analyzed by the Thermogravimetric (TG) and Brunauer-Emmett-Teller (BET) analysis. The synthetic
mechanism of the products with hierarchical structures was proposed. The obtained HDS-WO3 exhibits
Keywords:
excellent photocatalytic efficiency (84.9%), which is much higher than other WO3 sample under visible
Tungsten trioxide (WO3 )
Hierarchical
light illumination.
Visible-light © 2016 Published by Elsevier B.V.
Photocatalytic activity

1. Introduction template-based rheological phase reaction [19] and so on. With

Recently, the fabrication and design of inorganic hollow spheri-
cal materials with highly ordered architectures and well-defined
physical properties have been strongly motivated due to their
potential application in various fields, such as magnetism [1], optics
[2] and electronics fields [3], especially for waste water from tex-
tile, paper and residual dyes, which are not gladly biodegradable.
Semiconductor photocatalysts have been intensively investigated
in the last decades as it is potential in the applications to degrade
harmful pollutants and water [4,5]. Tungsten trioxide (WO3 ), as
an important n-type semiconductor with a band gap of 2.6 eV
[6], which have promise applications in gas sensing material [7],
photocatalytic [8], photoluminescent [9], and electrochromic [10].
Up to now, different morphologies of WO3 , including nanowires
[11], nanoflowers [12], nanotube [13], nanocuboids [14], hexago-
nal nanodisks [15] and hollow spheres [16] have been successfully
fabricated by microemulsion [17], hydrothermal reaction [18],
∗ Corresponding author at: State Key Laboratory of Hollow-Fiber Membrane Mate-
rials and Membrane Processes, Tianjin, 300387, PR China.
∗∗ Corresponding author at: School of Materials Science and Engineering, Tianjin
Polytechnic University, Tianjin, 300387, PR China.
E-mail addresses: dqingchu@163.com (D. Chu), wanglimin@tjpu.edu.cn
(L. Wang).
the rapid development of industry, the hazardous organic dye have
become a serious problem which is harmful to human health and
safety [24]. Photocatalytic technology was proved to be an efficient
pathway to degrade those organic pollutants. Nevertheless, to the
best of our knowledge, the obtained double-shell WO3 structures
exhibit excellent photocatalytic efficiency, which is much higher
compare to other paper. For instance, Chen et al. prepared hierar-
chical WO3 hollow shells with enhanced photocatalytic activity for
the degradation of organic contaminants [16]. Yu group reported
the enhanced activity of flower-like WO3 for the photodegradation
of dye [24]. Fujii et al. prepared Pt-loaded WO3 with different types
of morphology and photocatalytic degradation of methylene blue
[25].
Generally, multiple-shell nanostructures were preferred to
serve as sacrificial templates in fabricating core-shell nanostruc-
tures. While in this study, freshly-synthesized metal salts were
selected as the templates in preparing hierarchical double-shell
WO3 structures. Herein, we present a convenient and simple route
to prepare the uniform hierarchical double-shell WO3 superstruc-
tures. These microspheres dehydrated gradually during annealing
and transferred to monoclinic WO3 when annealed at 550 ◦ C. The
as-prepared hierarchical double-shell WO3 consisting of two shells
with the thickness of the outer shell and inner shell ∼300 nm
and ∼400 nm, respectively. The synthesis mechanism of the prod-
ucts with hierarchical structures was proposed. With regard to the

http://dx.doi.org/10.1016/j.apsusc.2016.10.181
0169-4332/© 2016 Published by Elsevier B.V.
 Z. Wang et al. / Applied Surface Science 396 (2017) 492–496
Fig 1. SEM, TEM images and XRD pattern of the as-synthesized HDS-WO3 : (a) overall product morphology; (b) a close-up image of an individual HDS-WO3 ; (c) a magnified
TEM image; (d) a representative XRD pattern recorded for the HDS-WO3 .
potential applications, the as-synthesized WO3 were also measured
for the photocatalytic activity of degradation of MB aqueous solu-
tion under the visible light illumination.
2. Experimental
2.1. Chemicals and synthesis of the samples
All chemicals were of analytical grade and used without fur-
ther purification. In a typical synthesis, 2 mmol of calcium chloride
dihydrate (CaCl2 ·2H2 O) was added into 10 mL deionized water to
form solution A, Then 1.2 mmol of Sodium Tungstate Dihydrate
(Na2 WO4 ·2H2 O) was added into another 10 mL deionized water to
form solution B. Next, solution B was rapidly mixed with solution
A to form a turbid liquid, which was disposed under continuous
magnetic agitation for another 45 min. Finally, the obtained prod-
ucts were collected by centrifugation, washed several times with
deionized water and ethanol, and dried in vacuum at 60 ◦ C for 12 h.
To prepare hierarchical double-shell WO3 microspheres, the as-
synthesized CaWO4 was soaked in HNO3 (4 mol/L) for 48 h at room
temperature, followed by calcination at 550 ◦ C for 2 h, resulting in
yellow powder.
2.2. Characterization
The phase and structure of the products were characterized by
using X-ray diffraction (XRD, D8 DISCOVER with GADDS version of
BRUCK Company of Germany), and scanning electron microscopy
(SEM, Qunanta 200, FEI). The specific surface area (SBET ) of the
samples was measured on a Micromeritics JW-BK (Beijing) ana-
lyzer and evaluated using the multipoint Brunauer–Emmett–Teller
(BET) method. For the uncalcined sample, thermogravimetry (TG)
was carried out under Ar atmosphere with a temperature ramp
of 10 ◦ C/min from room temperature to 600 ◦ C. And the diffuse
493
reflectance spectra were measured by a UV–vis spectrometer (TU-
1901, Beijing).
2.3. Photocatalysis measurement
The photocatalytic activity of the samples was carried out by the
degradation of MB under visible light irradiation. Typically, 100 mg
of WO3 powder was added into 100 mL MB aqueous solution
(20 mg/L) in a reactor at ambient temperature. Prior to irradiation,
the mixture was magnetically stirred in the dark for 30 min to reach
the adsorption/desorption equilibrium. The photocatalytic process
was irradiated by Xeno lamp (100 W). After visible light irradia-
tion for some time, the reaction solution was filtrated to measure
the concentration change of MB by recording the changes of the
intensity of absorption peak at 665 nm using a UV–vis spectropho-
tometer.
3. Results and discussion
3.1. Structure and morphology
The morphology and structure of the as-prepared products were
investigated by SEM, TEM and XRD analysis. A panoramic morphol-
ogy of the product is displayed in Fig. 1a, indicating the high yield
and uniformity. It reveals that the as-synthesized products are com-
posed of nearly monodisperse spherical particles with average size
5 ␮m and some broken spheres could also be observed from the
image. Fig. 1b shows an individual broken hemisphere which can
be seen that the microsphere consists of two shells and the thick-
ness of the outer shell and inner shell are ∼300 nm and ∼400 nm,
respectively. Fig. 1c shows that the TEM images of the WO3 with
double-shell were obtained. Fig. 1d confirmed the phase of prod-
ucts was characterized by XRD analysis. Curve (i) shows the typical
XRD pattern of the as-synthesized, which can be indexed well to the
494 Z. Wang et al. / Applied Surface Science 396 (2017) 492–496
Fig. 2. EDS and XPS patterns of HDS-WO3 : (a) a representative EDS spectra; (b) XPS survey spectrum; (c) XPS spectra of W4f region; (d) XPS spectra of O1 s region.
pure orthorhombic phase of WO3 ·H2 O (JCPDS Card No. 43-0679).
After calcination, all of the peaks of the double-shell nanostruc-
tures can be indexed to monoclinic WO3 nanostructure (JCPDS Card
No. 71-2141) [20] (curve (ii) in Fig. 1d), and no peaks of any other
phases are detected, indicating the formation of pure WO3 under
these experimental conditions.
The surface characteristics of WO3 have been assessed by Energy
Dispersive X-Ray Spectroscopy (EDS) and X-ray photoelectron
spectroscopy (XPS) in Fig. 2. The analysis is confirmed the com-
position of the product in Fig. 2a, it can be seen the existence of
elements W and O in the products. The resultant survey spectrum
is shown in Fig. 2b, it was revealed that the product contains mainly
W and O elements with a small amount of C element. The peak of
C1 s at binding energy of about 285.88 eV is due to the adventitious
hydrocarbon from the XPS instrument itself, which is in fact used
to calibrate peak position. Fig. 2c shows theW4f core level of the as-
prepared WO3 particles. It is a doublet, the W 4f7/2 line at 36.17 eV
and the W 4f5/2 line at 38.27 eV are associated with the W6+ oxi-
dation state. The O1 s region of the sample, shown in Fig. 2d, can
be fitted into two peaks. The minor one, located at binding energy
532.84 eV, is ascribed to the oxygen species adsorbed on the WO3
surface [23]. The major peak in the O1 s core level spectrum, which
is observed at binding energy 530.88 eV, is assigned to W O bond.
For comparison, the surface characteristics of WO3 ·H2 O were also
investigated by EDS and XPS in Supporting information (Fig. S1).
Therogravimetric (TG), Nitrogen adsorption-desorption
isotherm and corresponding pore-size distribution curves of
the obtained precursors are displayed in Fig. 3. According to the TG
result, Fig. 3a indicated that a major weight loss of 8.71% is observed
at temperatures ranging from 100 ◦ C to 300 ◦ C with the maximum
loss at ∼200 ◦ C in hydrated water. The slight weight loss observed
at temperatures between 300 ◦ C and 550 ◦ C may be attributed
to some final water decomposition occurring during the crystal-
lization of the amorphous phase [21]. The weight did not change
significantly over 500 ◦ C, which indicated that those organics had
been removed thoroughly. The nitrogen adsorption–desorption
isotherms of the hierarchical double-shell WO3 spheres are shown
in Fig. 3b. Hysteresis loops can be observed in the isotherms of the
sample, indicating the presence of mesopores in all samples [22].
The BET surface area of the as-prepared sample is calculated to be
25.06 m2 g−1 by the Brunauer–Emmett–Teller (BET) method. The
pore size distributions determined by the Barrett–Joyner–Halenda
(BJH) method are displayed in inset of Fig. 3b. The pore radius
distribution of samples shows an average of 17 nm. The results
indicated that this complicated double-shell spheres possess
various pores. This is important for expanding the application
range of double-shell WO3 spheres.
3.2. Formation mechanism
To study the formation process of the HDS-WO3 nanostructure,
samples which had soaked for 1 h, 6 h and 12 h were studied by
SEM, respectively. Three obvious evolution stages could be clearly
observed and are shown in Fig. 4. In the initial stage, samples con-
sisting of solid particles with well-defined spherical morphology
were shown in Fig. 4a. Fig. 4c shows that many nanoplates have
 Z. Wang et al. / Applied Surface Science 396 (2017) 492–496 495

Fig. 3. (a) TG curve of the as-synthesized WO3 ·H2 O under Ar atmosphere at a temperature ramp of 10 ◦ C/min; (b) Nitrogen adsorption and desorption and pore-size
distribution curve isotherms (inset) of the HDS-WO3 microspheres.

Fig. 4. The SEM images of the as-prepared HDS-WO3 microstructures under the different soaking times: (a) and (b) 1 h; (c) and (d) 6 h; (e) and (f) 12 h.

epitaxially grown from the surface of these spheres. By increas-
ing soaking time, evacuation of the particle interior became more
pronounced from Fig. 4e. On the basis of above analysis, we
can concluded that the homogeneous and regular morphologies
are probably formed through a mechanism similar to those pro-
posed for the formation of hierarchical double-shell WO3 spheres
[16,20]. During the nitric acid treatment, Ca2+ was removed from
CaWO4 , while the original sphere shape transformed into core-shell
structure consisting of platelet building blocks, and which clearly
displays the structure nature of freshly synthesized WO3 ·H2 O inter-
mediates without heat-treatment. Subsequently, the calcinations
process removed the water content and promoted the crystal-
lization of WO3 to form stable shells. The possible reactions are
described as follows:
CaWO4 + 2H+ → Ca2+ + WO3 ·H2 O (1)
496 Z. Wang et al. / Applied Surface Science 396 (2017) 492–496
Fig. 5. Curves of photocatalytic degradation rates (A) vs. irradiation time (t) for
the WO3 particles with different WO3 (A: blank; B: commerical; C: core-shell; D:
double-shell).
WO3 · H2 O calcination WO3 + H2 O
→ properties of WO3 center dot H2 O with different morphologies, Physica E 56
3.3. Photocatalytic properties
The photocatalytic activities of WO3 were examinated by mea-
suring the degradation on MB under visible light irradiation, and
the results were shown in Fig. 5. By contrast, the MB degradation
with core-shell WO3 spheres, the MB degradation with commercial
WO3 nanoparticles and the MB degradation without any catalyst
(blank experiment) under identical conditions were also examined.
The control experiment shows that the degradation rates of MB is
extremely slow without catalyst. It is worth mentioning that the
photocatalytic degradation of HDS-WO3 particles is much higher
than other morphologies of WO3 particles, which can be attributed
to the larger surface area of HDS-WO3 nanostructure.
4. Conclusions
In summary, hierarchical double-shell WO3 hollow spheres syn-
thesizing through a facile method by metal salts were selected as
the templates. Based on time-dependent experiments, a synthesis
mechanism of the products with hierarchical structures was pro-
posed. In addition, the photocatalytic activity experimental results
indicated that the degradation rate of HDS-WO3 is up to 84.9%,
which is much higher than other WO3
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apsusc.2016.10.
181.
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