Journal of Alloys and Compounds 651 (2015) 29e33

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Preparation of bamboo-shaped BiVO4 nanobers by electrospinning

method and the enhanced visible-light photocatalytic activity
Zhendong Liu a, Qifang Lu a, *, Cuiqing Wang b, Jinhua Liu a, Guoshuai Liu a
a
Shandong Provincial Key Laboratory of Processing and Testing Technology of Glass and Functional Ceramics, School of Material Science and Engineering,
Qilu University of Technology, Jinan 250353, PR China
b
Lunan Research Institute of Coal Chemistry, Jining 272000, PR China

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 16 June 2015
Received in revised form
28 July 2015
Accepted 16 August 2015
Available online 19 August 2015

Bamboo-shaped BiVO4 nanobers have been prepared by the electrospinning process followed by the
subsequent calcine of the electrospun precursor bers. The samples were characterized by thermogravimetric and differential scanning calorimetry (TGeDSC), fourier transform infrared spectroscopy (FT-IR),
Micro-Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission
electron microscopy (TEM) and UVevis absorbance spectroscopy. The results revealed that the bambooshaped BiVO4 nanobers with the diameter about 200 nm belonged to the monoclinic scheelite phase
and exhibited the excellent photodegrading properties of methylene blue (MB) solution under the visible
light irradiation.
2015 Elsevier B.V. All rights reserved.

Keywords:
BiVO4 nanobers
Bamboo-shaped
Electrospinning
Photocatalysts

1. Introduction
Nowadays, the research on the semiconductor photocatalysts is
very promising due to its potential application in solving the
environmental problems, and allowing the use of sunlight as the
energy source for the pollutant controlling [1]. In the past decades,
TiO2 as the brilliant photocatalyst has been studied by many researchers [2,3]. But the band gap of TiO2 (Eg 3.2 eV) is relative
large and it just can absorb the ultraviolet light which is only a
small part of the sunlight [4]. Thus, the use of visible light photons
constitutes the key point for searching the excellent photocatalysts.
Among the new photocatalysts recently proposed, BiVO4 has
drawn much attention because of its narrow band gap and high
photocatalytic properties [5]. There are three main phases of BiVO4:
tetragonal scheelite structure, tetragonal zircon structure and
monoclinic scheelite structure. Thereinto the monoclinic scheelite
structure (Eg 2.4 eV) was found to possess the best photocatalytic
properties [5,6]. Among the recent reports, various kinds of morphologies of monoclinic BiVO4 nanomaterials have been developed,
such as nanoparticles [7], quantum tubes [8], microtube [9],
nanosheets [10] et al. Electrospinning is a new cheap and simple

* Corresponding author.
E-mail address: luqf0110@126.com (Q. Lu).
http://dx.doi.org/10.1016/j.jallcom.2015.08.125
0925-8388/ 2015 Elsevier B.V. All rights reserved.

method to obtain the nanobers which own the uniform

morphology and high specic surface area [11]. For example, Liu
et al. have synthesized BiVO4 microribbons [12], while Cheng et al.
have prepared the porous BiVO4 bers [13] by electrospinning
process. But their products show the short length, large diameter
and low photocatalytic activity and have no novel morphology, and
also some of their raw materials are very expensive. However, in
the present paper, a simple electrospinning method obtaining
monoclinic BiVO4 phase with the controllable superne bambooshaped morphology nanobers was discovered and the photocatalytic activity for methylene blue (MB) degradation has also
been performed in details.

2. Experimental sections
2.1. Preparation of the spinnable precursor sols
All reagents were analytical-reagent (AR) grade and used
without further purication. In a typical experiment, 0.195 g
(0.4 mmol) Bi(NO3)3$5H2O and 0.2 g citrate acid were added into
1.5 mL deionized water with stirring to form a suspension. 0.0468 g
(0.4 mmol) NH4VO3 was dissolved in 1.5 mL hot deionized water
with stirring to form a solution. The above suspension was mixed
with the above solution, and then 0.5 mL hydrochloric acid (conc.

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Z. Liu et al. / Journal of Alloys and Compounds 651 (2015) 29e33

37%) was added to form a transparent solution. Meanwhile, polyvinylpyrrolidone (PVP, Mw 1,300,000) solution was obtained by
1 g PVP dissolved in 10 mL anhydrous ethanol. Finally, the transparent solution was mixed with the PVP solution to form the
spinnable precursor sols.
2.2. Electrospinning process and the calcination of samples
The precursor sols were drawn into an injector (20 mm inner
diameter) with a syringe needle. The distance between syringe
needle and collector was 30 cm. Infrared lamps were used to adjust
the temperature and humidity to 42  C and 25%, respectively. Then
the electrospinning voltage and the advance speed of the injector
was set as 20 kV and 2.25 mL/h, respectively. After electrospinning,
the obtained gel bers were heated to the desired temperature
(400  C, 500  C and 600  C) at the rate of 2  C/min and then keeping
for 1 h. After cooled to room temperature naturally, the nal
products were obtained.
2.3. Characterization
Thermogravimetry and differential scanning calorimeter
(TGeDSC) were implemented on Labsys evo STA Simultaneous
thermal analyzer (France) under air atmosphere in the range of
30e800  C. Fourier transform infrared spectroscopy (FT-IR) spectra
were investigated with a BrukerVertex 70 FT-IR spectrometer in the
range of 400e4000 cm1. The Raman spectra were measured by a
laser Raman spectrophotometer (JY-HY800) in the range of
300e1000 cm1. The X-ray diffraction (XRD) patterns of the samples were measured on a D8 ADVANCE X-ray diffractometer
(Bruker,
Germany),
using
monochromatized
Cu-Ka
(l 0.15418 nm) radiation with a scan range from 10 to 70 . The
accelerating voltage and the applied current were 40 kV and 40 mA,
respectively. The morphologies and microstructures of the obtained samples were analyzed by a FESEM-4800 eld emission
scanning electron microscope (SEM, Hitachi) and transmission
electron microscopy (TEM) image (JEOL JEM-2010F). The UVevis
spectrum of the sample was recorded on a UV-2550 spectrophotometer (Shimadzu) in the wavelength range of 400e800 nm.

Fig. 1. TGeDSC curves of the gel bers.

400  C is due to the decomposition of nitrate, citric acid and the PVP
side chains and about 45% weight loses in this step. The fourth one
(ca. 17%) in the range of 400e500  C results from the decomposition of main chain of PVP [12,14]. The total weight loss is 82%.

2.4. Photocatalytic activity measurement

The photocatalytic activities of the products were evaluated by
the degradation of methylene blue (MB) solution. A 500 W Xe lamp
was used to simulated sunlight irradiation and a cutoff lter
(l  400 nm) was used to lter the ultraviolet light. Circulating
water was inset to cool the temperature of the Xe lamp. The distance between the Xe lamp and the MB solution is 100 mm. 0.06 g
photocatalysts were put into 40 mL MB solution (20 mg/L). The
suspension was magnetically stirred in the dark for 30 min to
achieve the adsorptionedesorption equilibrium and then the
photodegradation experiment was started. 4 mL solution was
sampled every 30 min and centrifuged to remove the photocatalysts. The ltrates were analyzed by UVevis spectrum of MB
with a UV-2550 spectrophotometer. The ratio (C/C0) of MB concentrations was used to evaluate the photocatalytic performance.

Fig. 2. FT-IR spectra of the gel bers (a) and obtained samples calcined at 400  C (b),
500  C (c) and 600  C (d) for 1 h, respectively.

3. Results and discussion

TGeDSC curves of the gel bers were measured in the temperature range of 30e800  C, as shown in Fig. 1. Four stages of
weight losses can be found. The rst stage of weight losses (ca. 3%)
below 120  C is mainly attributed to the loss of ethanol and moisture. The second step (ca. 17%) from 120  C to 300  C due to the
removal of absorbed water [14]. The third loss stage from 300  C to

Fig. 3. Raman spectra of the obtained samples calcined at 400  C (a), 500  C (b) and
600  C (c) for 1 h, respectively.

Z. Liu et al. / Journal of Alloys and Compounds 651 (2015) 29e33

Fig. 4. XRD patterns of the obtained samples calcined at 400  C (a), 500  C (b) and
600  C (c) for 1 h, respectively.

31

According to the corresponding DSC curves, the exothermic peak at

300  C is due to the decomposition of citric acid and nitrate. The
exothermic peak at 400  C is attributed to the decomposition of the
side chain of PVP, while the exothermic peak around 500  C is
caused by the decomposition of PVP main chain [14].
Fig. 2 shows the FT-IR spectra of the gel bers and obtained
samples calcined at 400  C, 500  C and 600  C for 1 h. As can be
seen in Fig. 2a, the peaks from 950 to 3100 cm1 are down to the
characteristic vibration of PVP [15]. The peaks at 2962 and
2926 cm1 are due to the vibration of CeH bond and the 1663 cm1
peak can be attributed to the vibration of C]O bond, while the
1289 cm1 peak represented the vibration of CeN bond [16]. The
characteristic peaks of PVP still existed shown in Fig. 2b. The vibration at 3446 cm1 is due to the vibrations of eOH in the
adsorbed water, and the strong peak at 731 cm1 indicate the VO3
4
[10,17] (calcined at 500  C and 600  C). It can be seen that the organics were removed from the calcined samples at 500  C and
600  C for 1 h.
As is shown in the raman spectra (Fig. 3a), there was not the
obvious peaks in the samples calcined at 400  C for 1 h. The
emerged peaks observed in Fig. 3b and c were denoted to the
various vibrations of BiVO4. The most intensity peak at 827 cm1

Fig. 5. SEM images of gel bers (a), samples calcined at 400  C (b), 500  C (c and d) and 600  C (e) for 1 h and TEM image of the samples calcined at 500  C for 1 h (f), respectively.

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Z. Liu et al. / Journal of Alloys and Compounds 651 (2015) 29e33

Fig. 6. UVevisible diffuse reection spectra of the samples calcined at 500  C for 1 h
(a) and 600  C for 1 h (b).

assigned to the symmetric VeO stretching mode and the weak peak
at 710 cm1 and 640 cm1 were attributed to the long and short
asymmetric VeO stretching mode, respectively [18]. A doublet at
369 cm1 and 330 cm1 corresponded to the symmetric and
asymmetric bending vibrations of the VO4 tetrahedron, respectively [19].
Fig. 4 shows the X-ray diffraction patterns of samples calcined at
the different temperature. As is shown in Fig. 4a, there was no the
obvious crystallization diffraction peaks in the samples calcined at
400  C for 1 h. As for the patterns of the nanobers calcined at
500  C and 600  C, the emerged peaks all can well indexed to be the
monoclinic phase BiVO4 (JCPDS: 14-0688). The characteristic peaks
at 18.7, 19.0 , 29.0 , 30.6 , 53.3 were denoted to (110), (011), (121),
(040), (161) planes of monoclinic phase BiVO4, respectively. It is
found that with increasing the calcined temperature, the intensity
of the diffraction peaks becomes more and more high which indicates the crystallinity was improved with increasing the calcined
temperature and no diffraction peaks from other impurities are
observed.
From SEM images seen in Fig. 5a, the precursor gel bers are
randomly arranged and display a well-ned one-dimensional (1D)
ber structure. The diameter of the gel ber is about 400 nm and its
length is in the centimeter scale. The surface of the gel bers is

relatively smooth. The samples calcined at 400  C for 1 h (Fig. 5b)

do not show an obvious change, but the diameter of the bers
shrinks to approximately 300 nm which is due to the decomposition of inorganic salts and side chains of PVP template. Fig. 5c and
d shows the bamboo-shape of the samples calcined at 500  C for 1 h
with different magnications, and it can be clearly seen that the
diameter continue shrinks to ca. 200 nm. Meanwhile, the
morphology of the bers transform from brous to the bambooshape. This is due to that with the increasing the calcined temperature, PVP decomposed completely, and grain growth and
atomic diffusion of the BiVO4 bers became more active, allowing
for the reapportion of atoms to lower chemical potential status and
eliminating rough surface to lower the interfacial energy [20]. The
TEM image (Fig. 5f) of the samples calcined at 500  C for 1 h indicates that the typical 1D morphology can well correspond to the
SEM image in Fig. 5d. As can be seen in the SEM image of BiVO4
samples calcined at 600  C for 1 h (Fig. 4e), the 1D structure was
destroyed and the bers cracked to rods.
UVevis diffuse reectance spectra of the obtained products
calcined at 500  C and 600  C for 1 h are shown in Fig. 6. It was
observed that all the samples exhibited the absorption in the visible
light range, but the absorbance of the samples calcined at 500  C is
higher than that of the samples calcined at 600  C for 1 h. The Eg
value can be estimated by a classical Tauc approach according to the
following equation:

n=2

Ephoton K Ephoton  Eg
Ephoton indicates the discrete photon energy, K is absorption coefcient constant and Eg shows the band gap energy. The value of n is
1 due to the direct band gap semiconductor of BiVO4 [21]. From the
equation, the Eg of the samples calciend at 500  C is about 2.45 eV,
and 2.46 eV for the samples at 600  C.
The photocatalytic activities of the samples were evaluated by
the degradation of MB solution under the visible light irradiation.
For comparison, the degradation abilities of the different samples
were measured under the same experimental conditions. As The
absorption spectra of MB solution used the samples calcined at
500  C and 600  C for 1 h as the photocatalysts were shown in
Fig. 7a and b, respectively. An obvious blue shift can be observed in
the spectra which resulted from N-demethylation of MB and
oxidative degradation occurred concomitantly [22]. The corresponding decomposition rates of the samples calcined at 500  C
under the visible light irradiation for 4 h shown in Fig. 7c was 87%
which is much higher than that of samples calcined at 600  C (68%).

Fig. 7. UVevis spectra of MB solution degraded by the samples calcined at 500  C (a) and 600  C (b) for 1 h, respectively. Photodegradation curves of MB in the presence of the
samples calcined at 500  C and 600  C for 1 h (c).

Z. Liu et al. / Journal of Alloys and Compounds 651 (2015) 29e33

4. Conclusion
The bamboo-shaped BiVO4 nanobers were prepared by electrospinning process followed by the calcined at 500  C for 1 h of the
electrospun precursor bers. They owned the enhanced visible
light photocatalytic activities. This study demonstrated that this
kind of bamboo-shaped BiVO4 nanobers is a very promising
candidate for the development of high photocatalysis performance
for the environmental and energy applications.
Acknowledgment
This work was supported by the National Natural Science
Foundation of China (Grant No. 51172133), Natural Science Foundation of Shandong Province (Grant No. ZR2013BQ001), Project of
Independent Innovation of University Institute of Jinan (Grant No.
201311034) and Project of Shandong Province Higher Educational
Science and Technology Program (Grant No. J13LA01).
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