Advanced Materials Research Vols 148-149 (2011) pp 1469-1472 Online: 2010-10-27

© (2011) Trans Tech Publications, Switzerland

doi:10.4028/www.scientific.net/AMR.148-149.1469

Synthesis, Characterization and Photocatalytic Activities of Bismuth

Vanadate by Facile Co-precipitation Method

Chaojun Liu and Yuehua Xu*

Institute of Biomaterial, College of Science, South China Agricultural University, Guangzhou
510642, China
xuyuehua@scau.edu.cn (Yuehua Xu); liu88320558@163.com (Chaojun Liu)

：BiVO4, Monoclinic, Visible Light, Co-precipitation, Photocatalytic

Keywords：

Abstract ： Monoclinic BiVO4 photocatalysts were synthesized via facile and straightforward
co-precipitation method at room temperature without high temperature treatment and characterized
with X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), flourier transfer infrared
spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET), and transmission electron microscopy
(TEM). The results indicate that through proper selection of synthesis conditions, it is possible to
obtain high efficient BiVO4 nanoparticles. The as-prepared monoclinic BiVO4 photocatalysts have an
average crystallite size of about 20 nm with the particle size of about 20 to 50 nm. Their
photocatalytic activities were evaluated by decolorization of rhodamine B in aqueous solution under
visible light irradiation, and the relationship between the photocatalytic activity of BiVO4 and their
physicochemical properties were investigated.

Introduction
Photocatalysis is a promising technology for water and air purification and remediation. Photocatalyst
TiO2 has been extensively investigated because of its nontoxicity, high chemical stability,
photostability, relatively low cost, and strong oxidizing power. However, TiO2 can only be excited by
ultraviolet radiation that occupies about 4% of the solar light due to its wide bandgap (3.2 eV for
anatase). Visible-light-driven photocatalysts have attracted much attention because the visible-light
(400 nm < λ < 800 nm) forms a major part of the solar spectrum. Therefore, the development of
efficient visible-light-driven photocatalysts has become one of the most important topics in
photocatalysis research, such as Ce/N/TiO2 [1], N/TiO2 [2], In2O3-CaInO4 [3], InVO4 [4], NiO-CaO
[5], BiOX(X=Cl, Br, I) [6], CeO2-Bi2O3 [7], γ-Bi2MoO6 [8], Bi2WO6 [9], and BiVO4 [10]. Among
them, bismuth vanadate (BiVO4) has received special attention for its good chemical properties,
nontoxicity, photochemical properties and thermostability.
BiVO4 is a polycrystalline compound in three different crystalline forms, i. e. tetragonal zircon,
monoclinic scheelite and tetragonal scheelite [11]. A number of preparation techniques for BiVO4
have been investigated during the past decade for photocatalytic applications, such as solution
combustion synthesis method [12], hydrothermal method [14], surfactant-assisted hydrothermal
method [13], and so on. However, these methods need extra energy and other assistance. Here, we
report a facile and straightforward co-precipitation method at room temperature to synthesize
monoclinic BiVO4 nanoparticles with large specific surface area and regular morphology. The
visible-light-driven photocatalytic activity of BiVO4 nanoparticles was evaluated by the degradation
of rhodamine B (RhB).

Experimental
Preparation of BiVO4 powders. Bismuth nitrate pentahydrate (Bi (NO3)3·5H2O) was dissolved in
50 mL of 1.34 mol L−1 acetic acid solution, and ammonium metavanadate (NH4VO3) was prepared by
dissolving 50 mL of (0.25 to 2.25) mol L−1 NaOH solution at room temperature. And then, two above

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1470 Manufacturing Processes and Systems

solutions were mixed ultrasonically together to obtain a stable and yellow homogeneous solution.
Lastly, the yellow powders were obtained after filtering, washing with distilled water, and drying in an
oven at 70°C. All BiVO4 samples prepared with 0.25 to 2.25 mol L−1 NaOH solution were labeled as
0.25 BiVO4, 0.50 BiVO4, 1.00 BiVO4, 1.75 BiVO4, and 2.25 BiVO4, respectively, for the sake of
convenience in discussing the results.
Characterization. X-ray diffraction (XRD) spectra were recorded with a MSAL XD-2
diffractometer (λ = 0.15406 nm) using Cu Kα radiation. FT-IR spectra were performed using a
Nicolet-510P infrared spectrophotometer. Diffuse reflectance spectra were measured using a
HITACHI U-2550 UV-Vis spectrophotometer, and diffuse reflectance spectra were referenced to
BaSO4. The morphology was characterized by scanning electron microscopy (SEM, FEI-XL30). The
Brunauer-Emmett-Teller (BET) surface area of the samples was determined by nitrogen
adsorption-desorption isotherm measurements at 77K on a nitrogen adsorption apparatus
(Micromeritics N5).
Photocatalytic activity test. Photocatalytic activities of the samples were determined by
decolorization of RhB under visible light irradiation. A 13W LED light was used as light source and
set about 11cm above the RhB aqueous solution. Experiments were carried out as follows: 0.2 g
photocatalyst was added into 200 mL of 5 mg L−1 RhB solution. Before illumination, the solution was
stirred and bubbled with oxygen for 1 h in order to reach the adsorption-desorption equilibrium. At
1 h intervals, about 10 mL suspensions were collected, and then centrifugated to remove the
photocatalyst particles. The filtrates were analyzed with a spectrophotometer by measuring its
absorbance at 554 nm.

Results and Discussion

TEM analysis. Fig. 1 shows TEM images of 0.25 and 0.50 BiVO4. The TEM images show that the
particle size is about 20 to 50 nm, and this result reveals that BiVO4 nanoparticles can be fabricated by
this method.

(a) (b)

Fig. 1 TEM images of (a) 0.25 BiVO4 and (b) 0.50 BiVO4.

XRD analysis. Fig. 2 shows X-ray diffraction patterns of BiVO4 powders prepared with different
concentration of NaOH. It is showed that the crystallinity of BiVO4 increases with the decreasing of
NaOH concentration except 2.25 BiVO4. 1.75 BiVO4 is poorly crystallized, and the other samples are
well crystallized. Except 2.25 BiVO4, the diffraction peaks of all BiVO4 agree well with those of the
pure monoclinic BiVO4 according to the JCPDS No. 14-0688, indicating that well-crystallized
monoclinic BiVO4 can be directly prepared at proper acidic solution using co-precipitation method
without high temperature treatment.
 Advanced Materials Research Vols. 148-149 1471

6000
90
5000 80

4000 70
Intensity

2.25 60
3000
1.75 50

R/%
2.25
2000 1.00 40 0.50
1.75
30 0.25
0.50
1000
20 1.00
0.25
0 10
0
20 30 40 50 60 70 80
200 300 400 500 600 700 800
2theta/o
Wavelength/nm

Fig. 2 XRD patterns of BiVO4 prepared Fig. 3 DRS spectra of BiVO4 prepared
with various NaOH concentration. with various NaOH concentration.

DRS analysis. Fig. 3 gives the diffuse reflectance spectra (DRS) that show the influence of NaOH
concentration on the UV-vis absorption. It is found that the visible absorption in the range of 650 to
800 nm almost increased with increasing NaOH concentration, except 2.25 BiVO4. However, the
red-shift of absorption edge increases with decreasing NaOH concentration.
FT-IR analysis. Fig. 4 shows FT-IR spectra of BiVO4 prepared with NaOH concentration range
from 0.25 to 2.25 mol L−1. In all the FT-IR spectra, the strong absorption band at around 734 cm−1 is
assigned to the bending vibration of the tetragonal VO4 [14], and the weak band at 470 to 480 cm−1 is
ascribed to the Bi-O bond [15]. The strong band at about 3438 cm−1 and the band at 1635 cm−1 are
attributed to the OH stretching vibrations of free and hydrogen-bonded surface hydroxyl groups [16].
The intensities of the strong band at about 3438 cm−1 increase with the increasing of NaOH
concentration, indicating that the hydroxyl group amount increase with increasing NaOH
concentration.

100 1.00

0.95

80
0.90
T/%

C/C0

0.85
60 0.25 0.25
0.50 0.50
1.00 0.80 1.00
1.75 1.75
2.25 2.25
40
0.75

0.70
20 1 2 3 4 5
3500 3000 2500 2000 1500 1000 500
-1 Time/h
wavenumber/cm

Fig. 4 FT-IR spectra of BiVO4 prepared Fig. 5 Photocatalytic decolorization of RhB over
with various NaOH concentration. BiVO4 prepared with various NaOH concentration.

Photocatalytic activity. Fig. 5 presents results for the photocatalytic decolorization of RhB using
BiVO4 prepared with different NaOH concentration. It is found that the photocatalytic activities of
BiVO4 samples for decolorization of RhB are different, and 0.50 BiVO4 exhibits the best
photocatalytic activity, indicating that the NaOH concentration played an important role in the
photocatalytic activity of BiVO4. 1.75 BiVO4 shows the worst photocatalytic activity because of its
poor crystallinity. The specific surface area of 0.25 BiVO4 is 21.6 cm2 g−1, bigger than that of 0.50
BiVO4 (20.3 cm2 g−1), and 0.25 BiVO4 also exhibits a greatest red-shift compared with other BiVO4
1472 Manufacturing Processes and Systems

photocatalysts. However, the photocatalytic activity of 0.25 BiVO4 is not good, probably due to its
lowest concentration of surface hydroxyl groups according to FT-IR spectra, which can be oxidized to
generate highly reactive hydroxyl radicals
OH. The best photocatalytic activity of 0.50 BiVO4 might
be ascribed to good crystallinity, big specific surface area, large surface hydroxyl group content, and
appropriate light absorption ability. On the basis of the above analysis, the photocatalytic activities of
as-prepared BiVO4 are influenced by crystallinity, particle size, specific surface area, surface
hydroxyl group concentration, and light absorption ability.

Conclusions
BiVO4 photocatalysts were synthesized by facile and straightforward co-precipitation method at room
temperature. The as-prepared BiVO4 photocatalysts exhibit the typical monoclinic scheelite structure.
0.50 BiVO4 exhibits the best photocatalytic activity, and the photocatalytic activities of as-prepared
BiVO4 are influenced by crystallinity, particle size, specific surface area, surface hydroxyl group
content, and light absorption ability. Therefore, the method developed here is an economical and
efficient method for preparing visible-light-driven BiVO4 photocatalysts.

Acknowledgements
The authors would like to thank Guangdong Science & Technology Development Foundation, and
the key Academic Program of the 3rd phase “211 Project” of South China Agricultural University
(2009B010100001).

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Manufacturing Processes and Systems
10.4028/www.scientific.net/AMR.148-149

Synthesis, Characterization and Photocatalytic Activities of Bismuth Vanadate by Facile Co-

Precipitation Method
10.4028/www.scientific.net/AMR.148-149.1469

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