View Article Online / Journal Homepage / Table of Contents for this issue

CrystEngComm

Dynamic Article Links <

Cite this: CrystEngComm, 2011, 13, 2500

PAPER

Published on 03 February 2011. Downloaded by University of California - Santa Cruz on 29/10/2014 00:57:09.

www.rsc.org/crystengcomm

BiVO4 nanoleaves: Mild synthesis and improved photocatalytic activity for

O2 production under visible light irradiation
Zhiqiang Wang,a Wenjun Luo,ab Shicheng Yan,a Jianyong Feng,b Zongyan Zhao,a Yisi Zhu,b Zhaosheng Li*abc
and Zhigang Zou*ac
Received 31st October 2010, Accepted 21st December 2010
DOI: 10.1039/c0ce00799d
Nano-leaf bismuth vanadate (BiVO4), which acts as an active photocatalyst for O2 evolution under
visible light irradiation, was synthesized by a wet chemical method. The BiVO4 photocatalyst was
obtained by the reaction of Bi(NO3)3$5H2O and NH4VO3 at a low temperature (60  C). Both the
morphology and the crystal phase of the synthesized product can be tuned by changing the
concentrations of the precursor. The O2 evolution activity of BiVO4 nano-leaves from photocatalytic
water splitting under visible light irradiation ( l >420 nm) is significantly higher than that of the BiVO4
sample synthesized by a traditional solid state reaction method, and the activity can be further
improved by annealing the samples.

Introduction
With the background of the energy crisis and environmental
concerns, intensive and growing attention has been paid to
photocatalytic water splitting by the direct utilization of solar
energy.1 The development of active photocatalysts, which can
directly split water into H2 and O2 under visible light irradiation,
remains one of the most challenging tasks for solar-energy
utilization. An alternative is to treat the water splitting reaction
in terms of two coupled half-reactions, which evolve H2 or O2
separately from aqueous solutions containing sacrificial
reagents.2,3 Oxygen evolution from water oxidation is more
difficult in the coupled half-reactions, because the formation of
one O2 molecular requires the transportation and reaction of
four electrons or holes.46 Therefore, highly active photocatalysts
for O2 evolution are crucial for the utilization of solar energy.
BiVO4 has been found to be one of the photocatalysts that
exhibits high activity for photocatalytic O2 evolution under
visible light irradiation.710 Various methods have been utilized
to prepare BiVO4 photocatalysts. The conventional synthesis
method is a solid-state reaction conducted at 700  C or
higher .7,11 It is easy to form defects in the BiVO4 crystals because
of volatilization at high temperature, and these defects would
affect the photocatalytic activity.8 Wet chemical methods are

a
Ecomaterials and Renewable Energy Research Center (ERERC),
Department of Physics, Nanjing University, Nanjing, 210093, P.R.
China. E-mail: zsli@nju.edu.cn; zgzou@nju.edu.cn
b
Department of Materials Science and Engineering, Nanjing University,
Nanjing, 210093, P.R. China
c
National Laboratory of Solid State Microstructures, Nanjing University,
Nanjing, 210093, P.R. China
Electronic supplementary information (ESI) available. See DOI:
10.1039/c0ce00799d

2500 | CrystEngComm, 2011, 13, 25002504

often used to prepare nanostructured BiVO4 such as star-like,12

nano-ribbon,17 nano-sheet,18 nanotubes,19 hyperbrached,20
mesoporous21 and hierarchical nanostructures,22 which show
higher activities than the samples synthesized by the solid-state
reaction, this is due to two reasons.8,1222 One is avoiding
volatilization at high temperature and decreasing the defect
formation. The other is that nanostructures often have short
transferring distance of photoinduced carriers (electron or holes)
from the place where they are excited to the active sites on the
surface of the material.15,16
However, most of the synthesis methods reported require
harsh conditions, such as using concentrated hydrochloric acid,
or in relatively high temperatures (160  C), etc. Here we report
a moderate method to synthesize novel BiVO4 nano-leaves at 60

C in a standard atmosphere, without any acid. In the current
method, a colloid intermediate was involved and the final crystal
was grown from the colloid directly, so the use of concentrated
acid to solve the precursors and high reaction temperatures was
avoided. The crystal phase, morphology, and structure of the
selected samples were characterized by X-ray diffraction (XRD),
scanning electron microscope (SEM), transmission electron
microscope (TEM), selected area electron diffraction (SAED),
BET surface area analyzer, and Ultraviolet-visible diffuse
reflectance spectra. X-ray photoelectron spectroscopy (XPS)
measurements were carried out to identify the chemical states of
the metals in the samples. Moreover, water splitting experiments
under visible light irradiation were carried out to investigate the
photocatalytic O2 evolution activity of the as-prepared samples.

Experimental section
In a typical synthesis procedure, an equal mole amount of
Bi(NO3)3$5H2O, NH4VO3, and 4 g polyethylene glycol 4000
This journal is The Royal Society of Chemistry 2011

View Article Online

Published on 03 February 2011. Downloaded by University of California - Santa Cruz on 29/10/2014 00:57:09.

Table 1 The synthesis conditions of the samples

Sample S-1
Sample S-2
Sample S-3
Sample S-4
Sample S-5
Sample S-6
Sample S-7

Bi(NO3)3$5H2O

NH4VO3

Stirring
time

Reaction
condition

0.1 mmol
0.5 mmol
1 mmol
2 mmol
4 mmol
2 mmol
0.5 mmol

0.1 mmol
0.5 mmol
1 mmol
2 mmol
4 mmol
2 mmol
0.5 mmol

3h
3h
3h
3h
3h
3h

Sealed beaker
Sealed beaker
Sealed beaker
Sealed beaker
Sealed beaker
Opened grooves

(PEG4000) was added into 320 mL distilled water and stirred for
3 h at 20  C, to produce a colloid. Next, the colloid was poured
into a beaker and sealed with a plastic film. After that, the beaker
was put in an electronic oven and kept at a temperature of 60  C
for 24 h. The final product was washed and centrifuged several
times with water, then dried in the oven at 60  C. The amount of
Bi(NO3)3$5H2O and NH4VO3 was varied to investigate the effect
on the final product. The detailed experimental parameters are
listed in Table 1. Sample S-6 was synthesized by a slightly
modified method, the colloid was not sealed in a beaker but
dropped into horizontally set flat-bottomed plastic grooves
(the area of every groove is 4  10 4 m2), 2 mL per groove. In
order to investigate the colloid involved in the synthesis procedure, a sample of the colloid was washed and centrifuged several
times with water and dried by a freeze dry system to prevent any
further crystallization. This was noted as sample S-7.
XRD measurements were performed on a Rigaku Ultima III
X-ray diffractometer using Cu Ka radiation. Morphology of the
samples was obtained by employing a scanning electron microscope (FEI Nova NanoSEM 230, USA). All the SEM images
were taken when the samples were spread on the FTO (SnO2 : F)
substrate. TEM images and selected area electron diffraction
patterns (SAED) were obtained by employing a TEM (JEOL
JEM-2100, Japan) operated at 200 kV, and HRTEM (highresolution TEM) images were obtained by a TEM (FEI, Tecnai
F20, USA) operated at 200 kV. The specific surface area of the
samples was determined by BET measurements on nitrogen
adsorption at 196  C by an automatic surface area analyzer
(Micromeritics Tristar-3000, USA) after the samples had been
degassed in the flow of N2 at 150  C for 3 h. Ultraviolet
(UV)-visible diffuse reflectance spectra of the photocatalysts was
measured by using a UV-visible spectrophotometer (UV-2550,
Shimadzu, Japan). XPS data was collected on a Thermo fisher
scientific K-Alpha instrument.
The photocatalytic O2 evolution from aqueous silver nitrate
solution was carried out in a closed gas circulation system. The
photocatalyst (0.1 g) was dispersed in 270 ml 0.05 M AgNO3
aqueous solution. Before the illumination, the reaction system
was evacuated to remove the dissolved O2. The light source for
the catalytic reaction was a 300 W Xe arc lamp through a 420 nm
cut-off filter. Generated gas was analysed through an on-line gas
chromatograph with a TCD detector.

Results and discussion

In the stirring process of the sample synthesis, the
Bi(NO3)3$5H2O reacts with water to form slightly soluble
This journal is The Royal Society of Chemistry 2011

BiONO3. NH4VO3 is easily dissolved in water. BiVO4 was

obtained by the reaction of BiONO3 and VO3 . It is supposed
that only tiny BiVO4 clusters formed. Gradually, all the BiONO3
and the VO3 reacted and an amorphous colloid was formed
after stirring for 3 h. This colloid is the starting material of all the
final products.
SEM images of the sample S-2 show that it evolved into nanoleaves after the reaction at 60  C for 24 h (Fig. 1 a, b). Every piece
of the sample looks like four maple leaves joined at their petioles.
Branches grown on the petioles form a hyper-branched structure.
The thickness of the nano-leaves is about 30 nm, as shown in the
magnified SEM images (Fig. 1 e, f). The TEM images (Fig. 1c)
also confirm the morphology of the nano-leaves in the sample. In
the SAED pattern (the inset of Fig. 1c) derived from a piece of
leaf, the patterns of the same form deviate from each other
slightly. We suppose that the main part of the leaf is a singlecrystal in the initial stage which suffered minor deformation at
the thin branches in the wash and centrifugation procedures.
SEM images of the other samples synthesized at various
concentrations of precursors are shown in Fig. 2. The sample S-1
is a mixture of nano-leaves and nano-particles (Fig. 2a). The

Fig. 1 SEM and TEM images of a representative sample (sample S-2).

(a) SEM image of a peace of leaf. (b) SEM image with large field of view.
(c) TEM image of a piece of leaf, the inserted picture is the SAED pattern
recorded from this whole piece of leaf. (d) HRTEM image of a leaf. (e)
Magnified SEM image of the leaves. (f) HRSEM image of the leaves. The
samples were put on the FTO substrate to facilitate taking the SEM
images.

CrystEngComm, 2011, 13, 25002504 | 2501

Published on 03 February 2011. Downloaded by University of California - Santa Cruz on 29/10/2014 00:57:09.

View Article Online

sample S-3 is nearly identical to sample S-2 and appears to be of

well defined nano-leaves (Fig. 2b). When the amounts of both
Bi(NO3)3$5H2O and NH4VO3 were increased to 2 and 4 mmol,
thick irregular micro-rods dominated the morphology (Fig. 2 c,
d). The sample S-6 is a pile of monodispersive cubic-like blocks
(Fig. 2 e, f) where every particle is constructed by eight smaller
cubic blocks. The formation of cubic-like blocks with pure
tetragonal phase (the phase is shown in next paragraph) is due to
its special synthesis condition: it is also grown from the same
colloid synthesized from 2 mmol of the precursors; the colloid is
concentrated as the water evaporates in the oven and provides
a dynamic change in concentration which results in the tetragonal BiVO4.
XRD was used to detect the phases of the samples, the results
of which are shown in Fig. 3. The samples S-1 and S-2 are in
a pure monoclinic phase, which matches well with the JCPDS file
14-0688 (Fig. 3a). The sample S-6 is in a pure tetragonal phase,
which is in agreement with the JCPDS file 14-0133 (Fig. 3h).
There is a mixture of monoclinic and tetragonal phases in S-3 and
S-4 and an unknown impurity appears in the sample S-5. In the
XRD patterns of samples S-1S-5, the relative intensity of the
main peaks of the monoclinic phase decreases and the tetragonal
phase increases with the amount of the precursors, which indicates that the concentration of the precursors will influence the

Fig. 3 XRD patterns of the samples S-1S-7 and standard JCPDS

spectra of monoclinic (JCPDS 14-0688) and tetragonal (JCPDS 14-0133)
phases of BiVO4.

Fig. 2 (a) SEM image of sample S-1. (b) SEM image of sample S-2. (c)
SEM image of sample S-4. (d) SEM image of sample S-5. (e)(f) SEM
image of sample S-6. The samples were put on the FTO substrate to
facilitate taking the SEM images.

2502 | CrystEngComm, 2011, 13, 25002504

phase of the product. When the concentration is low, the product

tends to form a monoclinic phase. When the concentration is
high, the tetragonal phase readily appears in the products.
Our experiments confirm that a longer stirring period during
the colloid formation time tends to produce more areas of the
tetragonal phase (see Fig. S1 and Fig. S2 of the ESI). The
relative XRD intensity of the (040)/(
121)planes of the monoclinic
BiVO4 in the samples grown from 0.12 mmol precursors is much
higher than the corresponding standard value of JCPDS file
14-0688 (Fig. 3 ae). This indicates that the samples of the BiVO4
nano-leaves have anisotropic growth. The SAED pattern recorded of a BiVO4 nano-leaf and the high resolution TEM reveal
that it grew preferentially perpendicular to the [010] direction.
This result is similar to the cases of the star-like BiVO4 and
BiVO4 nano-plates in ref. 10 and 12, indicating that the anisotropic growth of monoclinic BiVO4 is not rare.
To evaluate the photocatalytic activity of the synthesized
BiVO4, selected samples were used as photocatalysts to oxidize
water for the generation of O2 under visible light irradiation
(Fig. 4). For comparison, the O2 evolution activity of bulk BiVO4
synthesized by the solid state reaction in the method of ref. 11
was also tested under the same conditions. The BiVO4 nanoleaves have a much higher photocatalytic O2 evolution activity
than the sample synthesized by solid state reaction (SSR),
although the SSR sample absorbs a greater portion of visible
light, as illustrated in the UV-visible diffuse reflectance spectra
(Fig. 5). It is supposed that the electron-hole pairs generated in
the crystal of BiVO4 by irradiation have a lower probability of
This journal is The Royal Society of Chemistry 2011

View Article Online

Published on 03 February 2011. Downloaded by University of California - Santa Cruz on 29/10/2014 00:57:09.

Table 2 The BET surface area of the samples

Fig. 4 Photocatalytic O2 evolution activity under visible light irradiation ( l >420 nm) from an aqueous AgNO3 solution (0.05 M, 270 mL)
over various photocatalyst (0.1 g): Annealed BiVO4 nano-leaves (sample
S-2), BiVO4 nano-leaves (sample S-2), the sample synthesized from the
solid state reaction (SSR), the micro-rods (sample S-4), and the Cubiclike blocks (sample S-6).

recombination in nano-leaves than in bulk materials, the reasons

may be that: (1) the electron-hole pairs have a shorter distance
(less than 30 nanometres) from the place where they are excited
to the reactive sites on the surface of the catalyst (in other words,
the sample of nano-leaves shows a higher BET surface area than
the SSR sample, as illustrated in Table 2), and (2) the crystallinity
of the BiVO4 nano-leaves is better than the SSR sample which
would be generated with many more defects in the crystal by
volatilization due to the high temperature solid state reaction
process. The activity of the nano-leaves was improved several
times after 10 h of annealing and the annealing temperature was
optimized from 100 to 600  C (see Fig. S3 of the ESI). The
nano-leaf sample which annealed at 400  C showed the highest
O2 evolution activity, and the XRD pattern and SEM images are
shown in Fig. S4 and S5 of the ESI. After annealing, the XRD
pattern and morphology of the sample S-2 have no obvious

Samples

Annealed S-2

S-2

SSR

S-4

S-6

BET surface area (m2 g 1)

7.2

9.2

0.4

5.5

2.3

changes. It is supposed that the annealing procedure improved

the crystallinity of the BiVO4 nano-leaves, and that the photon
excited electron-hole pairs have less recombination centres than
in the un-annealed sample. The BET surface area of the nanoleaf sample that annealed at 400  C shows no significant decline
(Table 2). In the sample S-4, it can be seen from the SEM that
there are lots of micro-rods and a significant amount of nanoleaves, and the XRD pattern shows a mixture of monoclinic and
tetragonal phases. It is supposed that only the monoclinic
portion in sample S-4 contributes to its photocatalytic activity,
which is why the photocatalytic activity of sample S-4 is
relatively lower than that of the sample S-2, which composed of
only monoclinic nano-leaves. The tetragonal phase cubic-like
blocks (sample S-6) show no visible light photocatalytic O2
evolution activity. Tetragonal BiVO4 was often considered to
exhibit little or no visible-light driven photocatalytic activity
according to ref. 8,23.
For the purpose of analyzing the chemical composition and
oxidation states of the elements, XPS measurements were carried
out (see Fig. S6 of the ESI). The XPS spectra of the photocatalysts were similar. The peaks are identified as the spinorbit
split of Bi 4f7/2, Bi 4f5/2 signals, and V 2p3/2, V 2p1/2 signals, which
confirms the presence of each element. The positions of the fitting
peaks are comparable to that of the BiVO4 in ref. 18.

Conclusion
In summary, a simple and moderate method to synthesize
monoclinic BiVO4 nano-leaves was developed. Concentrated
precursors will produce and increase the portion of tetragonal
BiVO4, and the morphology of the sample will change to microrods or cubic-like blocks. The photocatalytic water splitting
activity of the BiVO4 nano-leaves under visible light irradiation is
much higher than that of the BiVO4 sample synthesized by the
solid state reaction due to the low dimension nature of the nanoleaves. The activity can be improved significantly by annealing
the BiVO4 nano-leaves at 400  C. The mild sample synthesis
method has potential to be utilized in the synthesis of low
dimensional multi-metal layered oxides.

Acknowledgements
The authors thank financial support from the National Basic
Research Program of China (No. 2007CB613305), China-Japan
cooperation project of science and technology (No.
2009DFA61090) the NSFC (Nos. 50732004, 21073090, and
20811140087), and NSF of Jiangsu Province (No. BK2008028).

References
Fig. 5 UV-visible diffuse reflectance spectra of the powder samples. (a)
Annealed BiVO4 nano-leaves (sample S-2). (b) BiVO4 nano-leaves
(sample S-2). (c) The sample synthesized from solid state reaction. (d) The
micro-rods (sample S-4). (e) The Cubic-like blocks (sample S-6).

This journal is The Royal Society of Chemistry 2011

1 A. Fujishima and K. Honda, Nature, 1972, 238, 37.

2 K. Maeda, M. Higashi, D. Lu, R. Abe and K. Domen, J. Am. Chem.
Soc., 2010, 132, 5858.
3 Y. Sasaki, H. Nemoto, K. Saito and A. Kudo, J. Phys. Chem. C, 2009,
113, 17536.

CrystEngComm, 2011, 13, 25002504 | 2503

Published on 03 February 2011. Downloaded by University of California - Santa Cruz on 29/10/2014 00:57:09.

View Article Online

4 M. W. Kanan and D. G. Nocera, Science, 2008, 321, 1072.

5 F. Saladin, I. Kamber, K. Pfanner and G. Calzaferri, J. Photochem.
Photobiol., A, 1997, 109, 47.
6 Z. Yi, J. Ye, N. Kikugawa, T. Kako, S. Ouyang, H. Stuart-Williams,
H. Yang, J. Cao, W. Luo, Z. Li, Y. Liu and R. L. Withers, Nat.
Mater., 2010, 9, 559.
7 A. Kudo, K. Ueda, H. Kato and I. Mikami, Catal. Lett., 1998, 53, 229.
8 A. Kudo, K. Omori and H. Kato, J. Am. Chem. Soc., 1999, 121,
11459.
9 D. Ke, T. Peng, L. Ma, P. Cai and K. Dai, Inorg. Chem., 2009, 48,
4685.
10 G. Xi and J. Ye, Chem. Commun., 2010, 46, 1893.

11 M. Gotic, S. Music, M. Ivanda, M. Soufek
and S. Popovic, J. Mol.
Struct., 2005, 744747, 535.
12 S. Sun, W. Wang, L. Zhou and H. Xu, Ind. Eng. Chem. Res., 2009, 48,
1735.
13 L. Zhou, W. Wang, L. Zhang, H. Xu and W. Zhu, J. Phys. Chem. C,
2007, 111, 13659.

2504 | CrystEngComm, 2011, 13, 25002504

14 W. Yin, W. Wang, M. Shang, L. Zhou, S. Sun and L. Wang, Eur. J.

Inorg. Chem., 2009, (2930), 4379.
15 S. S. Dunkle, R. J. Helmich and K. S. Suslick, J. Phys. Chem. C, 2009,
113, 11980.
16 D. Ke, T. Peng, L. Ma, P. Cai and P. Jiang, Appl. Catal., A, 2008, 350,
111.
17 F. Wang, M. Shao, L. Cheng, J. Hua and X. Wei, Mater. Res. Bull.,
2009, 44, 1687.
18 L. Zhang, D. Chen and X. Jiao, J. Phys. Chem. B, 2006, 110, 2668.
19 L. Ren, L. Jin, J. Wang, F. Yang, M. Qiu and Y. Yu, Nanotechnology,
2009, 20, 115603.
20 Y. Zhao, Y. Xie, X. Zhu, S. Yan and S. Wang, Chem.Eur. J., 2008,
14, 1601.
21 G. Li, D. Zhang and J. C. Yu, Chem. Mater., 2008, 20, 3983.
22 M. Shang, W. Wang, J. Ren, S. Sun and L. Zhang, CrystEngComm,
2010, 12, 1754.
23 Y. Guo, X. Yang, F. Ma, K. Li, L. Xu, X. Yuan and Y. Guo, Appl.
Surf. Sci., 2010, 256, 2215.

This journal is The Royal Society of Chemistry 2011