Journal of Hazardous Materials 181 (2010) 11021108

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Synthesis of monoclinic structured BiVO4 spindly microtubes in deep eutectic

solvent and their application for dye degradation
Wei Liu , Yaqin Yu, Lixin Cao, Ge Su, Xiaoyun Liu, Lan Zhang, Yonggang Wang
Institute of Materials Science and Engineering, Ocean University of China, Qingdao 266100, PR China

a r t i c l e

i n f o

Article history:
Received 15 January 2010
Received in revised form 11 May 2010
Accepted 27 May 2010
Available online 4 June 2010
Keywords:
Bismuth vanadate
Deep eutectic solvent
Microtube
Photocatalyst

a b s t r a c t
Monoclinic structured spindly bismuth vanadate microtubes were fabricated on a large scale by a simple ionothermal treatment in the environment-friendly green solvent of urea/choline chloride. The
as-prepared samples were characterized by XRD, SEM, TEM, IR and their photocatalytic activity was
evaluated by photocatalytic decolorization of rhodamine B aqueous solution under visible-light irradiation. As-obtained BiVO4 microtubes exhibit the spindly shape with a side length of ca. 800 nm and a wall
thickness of ca. 100 nm. The opening of these microtubes presents a saw-toothed structure, which is seldom in other tube-shaped materials. The formation mechanism of the spindly microtubes is ascribed to
the complex cooperation of the reactioncrystallization process controlled by BiOCl and the nucleationgrowth process of nanosheets induced by solvent molecules attached on the surface of microtubes. Such
spindly microtubes exhibit much higher visible-light photocatalytic activity than that of bulk BiVO4 prepared by solid-state reaction, possibly resulting from their large surface area and improved crystallinity.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Much attention has been focused on room temperature ionic liquids in recent years due to their successful applications as benign
solvents for organic chemical reactions, separations, electrochemical chemistry and materials chemistry [1,2]. In contrast to the
success of ionic liquids, the deep eutectic solvent (DES), which
exhibits very similar solvent properties to ionic liquids, is still in its
infancy [3,4]. DES is the mixture of two or more compounds and has
a lower melting point than that of either of its constituents. Examples of DES include the mixtures of quaternary ammonium salts
(e.g. choline chloride) with neutral organic hydrogen-bond donors
(such as amides, amines, and carboxylic acids) [59]. Unlike ionic
liquids, these eutectic mixtures are considered as the desirable
environment-friendly green solvents because they are nonreactive with water, biodegradable, and excellent solvents for a wide
variety of solutes. Furthermore, another advantage of DES over
ionic liquids is easy to prepare with low-cost raw materials, which
makes DES to be particularly desirable for applications in the largescale synthesis of new functional materials. In spite of the great
interest in incorporating inorganic self-assemblies into DES, the
number of works reporting on the use of DES in the synthesis of
micro/nanomaterials is still limited [1012].

Corresponding author. Tel.: +86 532 66781690; fax: +86 532 66781332.
E-mail address: weiliu@ouc.edu.cn (W. Liu).
0304-3894/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2010.05.128

Recently, the decomposition of harmful organic and inorganic pollutants using photosensitized semiconductors as catalysts
has attracted increasing attention [1315]. Of them, bismuth
vanadate (BiVO4 ) has been recognized as a strong photocatalyst
(bandgap: 2.4 eV) for pollutant decomposing due to its photocatalytic response to the visible-light region and relatively strong
oxidation properties for water splitting [1625]. Three crystalline
phases of BiVO4 materials have been reported, named as monoclinic scheelite, tetragonal zircon and tetragonal scheelite. Of
them, monoclinic BiVO4 exhibits much higher visible-light photocatalytic activity over the other forms, giving rise to more attentions
and wider researches. Besides crystalline form, the photocatalytic
property of BiVO4 also depends strongly on the microstructure of
particles. To further improve the visible-light photocatalytic activity, a few submicron- or nanometer-sized BiVO4 particles with
sheet, tube, rod or sphere shape have been prepared [2629].
However, surfactants or organic templates are generally added in
the reactions in order to control their microstructures, causing
the production of lots of acid-alkali wastewater containing refractory organics. Therefore, a new template-free and environmentally
benign green route is expected in the preparation of photocatalysts.
Since urea is one of the normal metabolites of mammals and
choline chloride is one kind of common food additives without
any environmental side-effects, the DES of urea/choline chloride, as
one pure environmentally compatible green solvent, absorbs more
attention. In this study, we report rstly the production of visiblelight-driven BiVO4 spindly microtubes in the deep eutectic solvent

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1103

of urea/choline chloride. The composition and microstructure of asprepared products are investigated and their photocatalytic activity
is also evaluated.
2. Experimental
2.1. Synthesis of spindly BiVO4 microtubes
All the chemicals in this study were used as received from
Shanghai Chemical Regent Factory of China without further purication. Distilled water was used in all experiments. The spindly
microtubes were prepared through a simple ionothermal method.
In the typical process, the deep eutectic solvents (2 g) were synthesized by heating a mixture of choline chloride and urea in the 1:2
molar ratio at 70 C for 30 min to a colorless liquid. Then 1 g water
was added into the solution to adjust the viscosity of the DES. After
magnetic stirring to homogenous liquid, Bi(NO3 )3 5H2 O (48.5 mg)
and NH4 VO3 (11.7 mg) were added into the above solution under
magnetic stirring. The light yellow aqueous solution obtained after
continuous vigorous stirring for 30 min was transferred into a 15mL Teonlined autoclave, which was lled with 80% of the total
volume. The autoclave was sealed and kept at 150 C for 15 h.
The nal light yellowish products were centrifuged, washed with
deionized water and absolute ethanol for several times, and then
dried at 80 C in air. For comparison, bulk BiVO4 particles were
also prepared by the traditional solid-state reaction (SSR-BiVO4 )
according to the previous literature [30].
2.2. Characterization
The powder X-ray diffraction (XRD) patterns of as-synthesized
samples were measured on a X-ray diffractometer (Bruker D8
ADVANCE) using monochromatized Cu K ( = 0.15418 nm) radiation under 40 kV and 100 mA. The particles were spread on a
glass slide specimen holder and the scattered intensity was measured between 10 and 70 at a scanning rate of 2 = 5 /min. The
morphologies and microstructures of as-prepared samples were
examined with scanning electron microscopy (SEM, JSM-6700F)
and equipped with an energy-dispersive X-ray spectroscope (EDS).
Transmission electron microscopy (TEM) observations were carried out on a JEOL JEM-2100 instrument with accelerating voltage
200 kV in bright-eld and selected-area electron diffraction (SAED)
modes. The specimens used for TEM studies were dispersed in
absolute ethanol by ultrasonic treatment. The sample was then
dropped onto a copper grid coated with a holey carbon lm and
dried in air. UVvis diffuse reectance spectroscopy (UVvis-DRS)
in the spectral range from 200 to 700 nm was performed with a
Hitachi U-3010 UVvis spectrometer. The baseline correction was
performed using a calibrated reference sample of barium sulfate.
The BrunauerEmmettTeller (BET) surface areas were estimated
with the use of a Micromeritics ASAP2010 Analyzer. IR spectra were
collected using a Digilab-FTS-80 spectrophotometer using pressed
KBr pellets of the samples. Photoluminescence spectra were measured by Fluorolog-3-P with 450 W Xe lamp.
2.3. Photocatalytic test
Rhodamine B (RhB), one of the N-containing dyes, which are
resistant biodegradation and direct photolysis, is a popular probe
molecule in the heterogeneous photocatalysis reaction. The evaluation of photocatalytic activity of the prepared samples for the
photocatalytic decolorization of RhB aqueous solution was performed at ambient temperature, as reported in our previous studies
[31]. Experimental procedures were as follows: the weight of catalysts used in each experiment was kept 0.2 g. A 250 mL beaker was
dried in an oven at 80 C for about 2 h to evaporate the water and

Fig. 1. XRD pattern of spindly BiVO4 microtubes prepared by ionothermal treatment

at 150 C for 15 h in the solvent of urea/choline chloride.

then cooled to room temperature before used. 100 mL RhB aqueous solution with a concentration of 1 105 M was added into
the beaker in each experiment, and then the photocatalyst powder
put into the RhB solution to form the homogenerous suspension by
ultrasonic bath for 5 min. A 500 W Xe lamp (10 cm above the beaker)
was used as the light source, and the beaker was covered with UV
cutoff lter to completely remove any radiation below 400 nm and
to ensure illumination by visible-light only. Prior to irradiation, the
beaker containing catalysts and RhB aqueous solution was kept
in the dark for 30 min to ensure the establishment of an adsorption/desorption equilibrium between catalysts and RhB molecules.
After irradiation for a designated time, the dispersion was ltered to
separate the photocatalyst particles, and the RhB concentration of
the ltrate were monitored by checking the absorbance at 553 nm
during the photo degradation process using the UVvis spectrophotometer.
3. Results and discussion
3.1. Characterization of spindly BiVO4 microtubes
The phase and purity of the products obtained under 150 C
for 15 h was investigated by the XRD measurement. As shown in
Fig. 1, all the diffraction peaks can be readily indexed to a pure
monoclinic scheelite phase BiVO4 of lattice constants a = 0.7331 nm,
b = 0.7331 nm and c = 0.6462 nm, which agrees with the reported
values of a = 0.7300 nm, b = 0.7300 nm and c = 0.6457 nm (JCPDS
No. 48-0744). No peaks for any other phases or impurities were
detected.
The morphology and microstructure of as-prepared BiVO4 particles were measured by the electron microscopy. The SEM image
(Fig. 2a) shows that the product is well-dened microtubes with
a length of 810 m, in which particles with other morphologies
cannot be observed. Close observation of the samples (Fig. 2b)
demonstrates that the individual tube exhibits a spindly shape with
a side length of ca. 800 nm and a wall thickness of ca. 100 nm.
Interestingly, the opening of these microtubes presents the novel
saw-toothed structure, which is seldom in other tube-shaped materials reported in previous literatures. Connected with tooth tip of
two openings, the distinct grooves on the rough surface of tubes can
be identied clearly and divide the tube into four long columns with
sharp heads. In this way, the hollow interior structure of products
can also be depicted as the encapsulation of such four long columns
in parallel. The corresponding TEM image (Fig. 2c) demonstrates
that the BiVO4 particles are spindle in shape with dentate openings, but limited information about the hollow interior structure of
as-prepared samples can be obtained due to the large particle size

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W. Liu et al. / Journal of Hazardous Materials 181 (2010) 11021108

Fig. 2. (a) Low magnication SEM image of as-obtained product; (b) Close observation of microtubes showing the hollow structure and wall thickness; (c) TEM image for a
single BiVO4 microtube; (d) the corresponding SAED pattern taken from the tooth tip part of the microtube.

and the strong electron absorption of heavy metal atom of Bi. The
selected-area electron diffraction (SAED) pattern (Fig. 2d) reveals
the single-crystal nature of the BiVO4 spindly tubes, and the ED
pattern can be indexed to the diffraction pattern of [0 1 0] zone axis
indicating a preferred (0 1 0) surface orientation of the tubes.
The EDS analysis (the percent content of the elements (wt%): O,
12.50%; V, 15.71%; Bi, 71.80%) reveals that the elemental composition of the spindly tubes is vanadium, bismuth, and oxygen with a
molar ratio of Bi:V = 3.36:3.38, which is very close to the Bi:V molar
ratio (1:1) in monoclinic BiVO4 . The BET surface area of spindly
BiVO4 samples is estimated to be ca. 3.46 m2 /g, which was much
higher than that of the reference SSR-BiVO4 sample of ca. 0.75 m2 /g.

To investigate the formation process of spindly BiVO4 microtubes, a detailed time course experiment was carried out. Fig. 3
shows the XRD patterns of time series samples. It can be seen from
Fig. 3a that only few weak reections of the precursors without

ionothermal treatment can be identied and are assigned to bismuth oxychloride BiOCl (PDF-2 No.06-0249). As the time increases
to 40 min, the peak intensity of BiOCl decreases obviously while a
new broad peak at 2 = 28 appears (Fig. 3b). After 1 h, the diffraction peaks of monoclinic BiVO4 can be clearly observed at 2 = 18.6
and 28.9 , and the remaining ones at 2 = 32.5 and 46.7 are
assigned to BiOCl (Fig. 3c). This indicates that the mixture phases
of monoclinic BiVO4 and BiOCl are produced in the sample after
treated for 1 h. With the time is prolonged to 2 h, the peaks corresponding to monoclinic BiVO4 become more and more dominant,
and the diffraction peaks corresponding to BiOCl disappear except
for few tiny peaks (Fig. 3d). After treated for 10 h, all crystal diffraction peaks can be indexed to be a pure monoclinic phase BiVO4
(Fig. 3e). When the time increases to 15 h, the XRD pattern of the
products are nearly the same as that of the 10 h one except for a
little intensity increasing (Fig. 3f). FT-IR absorption spectra of the
precursor and the samples prepared after ionothermal treatment
for 40 min, 1 h, 10 h and 15 h were also measured (Fig. 4). The spectrum of precursor demonstrates a weak absorption of (BiO) at

Fig. 3. XRD patterns of as-prepared BiVO4 powders at various treated time (a) precursors; (b) 40 min; (c) 1 h; (d) 2 h; (e) 10 h and (f) 15 h.

Fig. 4. (a) IR spectrum of the precursor and IR spectra of samples after ionothermal
treatment at 150 C for (b) 40 min, (c) 1 h, (d) 10 h and (e) 15 h in DES solution.

3.2. Formation of spindly BiVO4 microtubes

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around 529 cm1 , that can be interpreted as the presence of bismuth oxochloride [32]. The absorptions of 1 (VO4 ) and 3 (VO4 ) (at
around 751 cm1 ) can be attributed to the vanadium amorphous
phase and the band at 1637 cm1 may be assigned to the absorbed
CO2 in the air [29]. The remaining peaks including the broad peak
of (OH) at 3430 cm, the weak peaks of (CH2 ), (CH3 ) and (CH3 )
at 2923, 2856, 2958 and 1460 cm1 , and the peak of (N+ CH2 ) at
1400 cm1 , mainly correspond to choline chloride molecules [33].
Therefore, the precursor can be considered as the mixture of BiOCl,
vanadium amorphous phase and adsorbed organic molecules. With
prolonged ionothermal treatment, it is observed that the absorptions of 1 (VO4 ) and 3 (VO4 ) gradually increase in quantity, while
the peak for BiCl gradually decrease, which is in agreement with
the above XRD results. In addition, the peaks assigned to the choline
chloride disappear gradually with the increase of treated time, indicating that most of choline chloride molecules have been removed
during the crystallization process of BiVO4 . Whereas the enhanced
absorption bands of (N+ CH2 ) and (CH3 ) are observed in the
samples treated for 10 and 15 h, which may results from the oriented adsorption of a small amount of organic molecules on the
surface of samples.
The products collected at different reaction time were observed
by SEM. Fig. 5a shows that the precursors are well-dened BiOCl
nanosheets with a thickness of ca. 10 nm, part of which intersect
each other into a ower-like morphology (Fig. 5a inset). When
the reactive time is prolonged to 40 min, the nanosheet aggregates
evolve into ball-like compact microspheres with a diameter of ca.

1105

800 nm (Fig. 5b). A large amount of small protuberances appear

distinctly on the surface of these spheres (Fig. 5b inset), possibly
deriving from the overlapped nanosheets. When the time increases
to 1 h, a few small square-shaped microtubes growing out from the
conglomeration of microspheres can be observed clearly in Fig. 5c.
Close observation (Fig. 5d) of the corresponding crystal nuclei with
one concave surface (indicated by the arrow) suggests the initial
nucleation and growth process of as-prepared microtubes. As seen
from Fig. 5e, the product treated for 10 h consists almost of wholly
spindly microtubes with saw-toothed opening. No microspheres
can be found except for a quantity of irregular fragments adsorbed
on the surface of the tubes. Then, the microtubes begin to grow
longer. Finally, as the time is extended to 15 h, BiVO4 microtubes
with a length up to ca. 10 m are formed (Fig. 5f).
Based on above results, it is noticeable that BiOCl plays the crucial roles in forming the monoclinic BiVO4 microtubes. First, the
formation of BiOCl at the initial stage results in the heterogeneous
nucleation points for monoclinic phase BiVO4 . Second, BiOCl, as a
buffer, avoids the direct reaction between Bi3+ and VO3 in the
solvents, thereby controlling efciently the BiVO4 concentration
within the bulk solution. Generally, the simultaneously nucleation
and growth of large number of monoclinic phase BiVO4 seeds will
greatly reduce the concentration of BiVO4 in the bulk solution. Due
to the mediation effect of BiOCl, it could not provide enough reactants for the growth of BiVO4 crystals. Mass transportation to the
growing regions would lead to undersaturation in the central part
of the growing faces of each seeds, which causes the formation of

Fig. 5. Morphology evolution of as-prepared BiVO4 samples with the reaction time (a) precursors; (b) 40 min, (c, d) 1 h, (e) 10 h and (f) 15 h. The insets images of (a) and (b)
show the close observation of BiOCl aggregations.

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W. Liu et al. / Journal of Hazardous Materials 181 (2010) 11021108

Fig. 6. (a) Low magnication SEM image of samples treated for 10 h; (b) High magnication SEM image of the corresponding samples; (c) Close observation of the surface
of as-prepared samples treated for 10 h; (d) TEM photo of the nanosheets and the corresponding SAED pattern.

square-shaped crystal nuclei with hollow interior structure. This

can be conrmed by the concave surfaces observed in the initial
crystal nuclei of BiVO4 (Fig. 5d). Unlike BiVO4 microtubes reported
in previous literatures [28,29], however, the spindly shape of the
microtubes is obtained in our case, which possibly results from
the inductive effect of organic molecules in the solution. In the
growth process of microtubes, it is worthy of noting the presentation of the irregular fragments on the external/internal surfaces of
BiVO4 microtubes (Fig. 6a and b). The sheet nature of these fragments with the thick length of ca. 10 nm is observed clearly in
the corresponding TEM image (Fig. 6d) and the selected-area electron diffraction pattern (Fig. 6d inset) reveals that these nanosheets
crystallize in the form of monoclinic BiVO4 . Interestingly, high magnication SEM photo (Fig. 6c) demonstrates that these nanosheets
not only adsorb but also grow closely together with the wall of
microtubes, thereby giving rise to the rough surfaces and ragged
edges of BiVO4 microtubes. This nucleation and further growth of
nanosheets derives possibly from the inductive effect of solvent
molecules attached on the surface of microtubes. Since the polar
groups of the solvents such as hydroxyl of choline chloride and
carbonyl of urea can easily hydrogen bond with unsaturated bonds
and hydroxyl groups of crystal nuclei [5,6], part of solvent molecular can absorb on the surface of BiVO4 microtubes and thereby
induce the nucleation and growth of the nanosheets. This is also
supported by the above results of IR. With the rise of time, the
continuous and uneven growth of abundant nanosheets on various
parts of the microtubes causes possibly the formation of spindle
shape of BiVO4 microtubes eventually. The growth mechanism of
spindly BiVO4 , therefore, can be ascribed to the coexist effect of
the reactioncrystallization process controlled by BiOCl concentration and the nucleation-growth process of nanosheets induced by
solvent molecules adsorbed on the surface of microtubes.

Bi 6s and O 2p orbitals, whereas the conduction band is composed of V 3d orbitals. The charge transfer upon photo-excitation
is thus supposed to occur from Bi 6s and O 2p hybrid orbitals to
V 3d orbitals [36]. In order to investigate the electronic structure
of as-obtained spindly structure, UVvis absorption spectra were
measured for the spindly microtubes and SSR-BiVO4 samples. As
shown in Fig. 7, the spindly BiVO4 tubes have the strong absorption in UV and visible-light regions with the steep shape, which
indicates that the visible-light adsorption is due to the bandgap
transition [37]. According to the equation Ep = K(Ep Eg )1/2 (where
is the absorption coefcient, Ep is the discrete photoenergy, K
is a constant, and Eg is the band gap energy) [38]. The energy of
the band gap of BiVO4 photocatalyst could be thus obtained from
the plots of (h)2 versus photon energy (h), as shown in inset of
Fig. 7. The values estimated from the intercept of the tangents to the
plots were 2.48 and 2.44 eV for spindly BiVO4 tubes and SSR-BiVO4 ,
respectively. The increase in the bandgap of the as-prepared BiVO4
spindly microtubes could be indicative of the possible quantum

3.3. Band gap of the spindly BiVO4 microtubes

It is well known that the electronic structure of the semiconductor usually plays a crucial role in its photocatalytic activity [34,35].
Since the valence band (VB) of BiVO4 is composed of hybridized

Fig. 7. UVvis diffuse reectance spectra of spindly BiVO4 microtubes and SSRBiVO4 samples. Inset: plots of (h)2 vs. photon energy (h).

W. Liu et al. / Journal of Hazardous Materials 181 (2010) 11021108

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connement effects resulting from the nanosized building blocks

on the surface of spindly tubes.
Fig. 8 shows the comparison of PL spectra of SSR-BVO4 sample
and spindly BVO4 sample with excitation wavelength of 375 nm.
The PL emission spectra of two photocatalysts demonstrate the
main peaks at similar positions, but the PL intensity of spindly
BVO4 sample is lower than that of SSR-BVO4 sample, which clearly
indicates that the recombination between the hole and the electron is greatly inhibited [39]. Hence, it is indicated that the spindly
BiVO4 could be used as more efcient photocatalyst compared to
the SSR-BiVO4 catalysts.
3.4. Photocatalytic property of spindly BiVO4 microtubes
The visible-light photocatalytic activity of the spindly BiVO4
microtubes was evaluated by photocatalytic decolorization of RhB
aqueous solution. The blank experiment in the absence of catalysts
demonstrates a poor self-degradation of RhB under the visiblelight irradiation. After adsorption/desorption equilibrium between
RhB molecules and the samples, the concentration of RhB do not
change with increasing reaction time for every measurement using
BiVO4 samples under dark conditions without light illumination.
Therefore, the presence of both light illumination and BiVO4 catalysts is necessary for the efcient photocatalytic degradation of
RhB aqueous solution. These results also suggest that the degradation and decolorization of RhB aqueous solution is caused by
photocatalytic reactions on BiVO4 samples under the visible-light
illumination. Fig. 9 shows the UVvis spectra taken over time
during the photodegradation of RhB mediated by BiVO4 spindly
particles versus SSR-BiVO4 . Accompanying with the decrease of
absorption of RhB/BiVO4 suspension during the photodegradation
is the distinct blue-shift of its major absorption band, indicating
removal of ethyl groups one by one, which is in good accordance
with that in the literature [40]. After irradiation for 300 min, the
absorption blue-shifts from 552 to 498 nm in the presence of
the prepared spindly BiVO4 , indicating that RhB has being fully
demethylated, while in the same time period no distinct blue-shift
is observed for SSR-BiVO4 materials as catalyst. The results demonstrate that the BiVO4 spindly particles have superior photocatalytic
activities compared with the SSR-BiVO4 materials. The degradation
curves of RhB using spindly BiVO4 microtubes and SSR-BiVO4 as
photocatalysts are shown in Fig. 9 inset. The rate of photodegradation by spindly BiVO4 microtubes (98% in 300 min) is much
faster than that by SSR-BiVO4 (16%). Notably, the much-enhanced
visible-light-responsive photocatalytic property of spindly BiVO4
microtubes could be ascribed to their special tubular structure

Fig. 9. UVvis spectra taken over time during the photodegradation of RhB mediated
by BiVO4 spindly particles versus SSR-BiVO4 . The inset image is the degradation
curves of RhB without photocatalysts and using spindly BiVO4 microtubes and SSRBiVO4 as photocatalysts.

Fig. 10. RhB concentration changes with irradiation time over BiVO4 catalysts
ionothermally prepared for various time.

morphology. In one respect, the hollow internal structure and the

rough surface create large surface area, which can usually offer
more active adsorption sites and photocatalytic reaction centers;
in another respect, lots of surface defects and nanostructure on the
surface of microtubes can effectively promote the separation efciency of the electronhole pairs, thus improving their response to
visible-light.
In addition, the samples with prolonged ionothermal treatment
demonstrate the improved photocatalytic activity under visiblelight irradiation (Fig. 10). For example, the photocatalytic efciency
for RhB is only 33% in the presence of the sample ionothermally
treated for 1 h and 45% for the sample treated for 10 h, while the
highest rate of photodegradation (98%) is observed for the sample
ionothermally synthesized for 15 h. The possible explanation is due
to the improved crystallization performance of the samples with
the prolonged treated time. Generally, the particles with well crystallinity can decrease the defects inside the crystals, which allows
for the more efcient transfer of electronhole pairs, generated
inside the crystal, to the surface. Therefore, it is not surprising that
the well-crystallized spindly microtube shows the highest photocatalytic activity among the prepared samples.
4. Conclusions

Fig. 8. The room temperature photoluminescence (PL) spectra of SSR-BVO4 (a), and
spindly BVO4 (b) (ex = 375 nm).

Monoclinic structured BiVO4 microtubes with a length of ca.

10 m have been successfully fabricated in the deep eutectic
solvent of urea/choline chloride. As-obtained product exhibits a

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W. Liu et al. / Journal of Hazardous Materials 181 (2010) 11021108

spindly shape with the saw-toothed openings, which is seldom in

other tube-shaped materials reported in previous literatures. The
formation mechanism can be ascribed to the coexist effect of the
reactioncrystallization process controlled by BiOCl concentration
and the nucleation-growth process of nanosheets induced by solvent molecules attached on the surface of microtubes. Due to their
well crystallization and large surface area, the photodegradation
rate of as-prepared BiVO4 tubes can be up to 98% under the visiblelight irradiation for 300 min, which is much higher than that of
SSR-BiVO4 . This work might provide an environmentally benign
green method to the design of advanced photocatalytic materials with complex architecture for enhancing visible-light-driven
photocatalytic activity. It is also extended into design some novel
micro/nanostructures of other oxide materials, which is currently
underway.
Acknowledgement
This work is nancially supported by the Program for New Century Excellent Talents in University (NCET-08-0511).
References
[1] D. Simonsson, Electrochemistry for a cleaner environment, Chem. Soc. Rev. 26
(1997) 181189.
[2] T. Welton, Room-temperature ionic liquids. Solvents for synthesis and catalysis,
Chem. Rev. 99 (1999) 20712084.
[3] A.P. Abbott, G. Capper, D.L. Davies, R. Rasheed, V. Tambyrajah, Novel solvent
properties of choline chloride/urea mixtures, Chem. Commun. (2003) 7071.
[4] A.P. Abbott, D. Boothby, G. Capper, D.L. Davies, R.K. Rasheed, V. Tambyrajah,
Deep eutectic solvents formed between chorine chloride and carboxylic acids,
J. Am. Chem. Soc. 126 (2004) 91429147.
[5] E.R. Cooper, C.D. Andrews, P.S. Wheatley, P.B. Webb, P. Wormald, R.E. Morris, Ionic liquids and eutectic mixtures as solvent and template in synthesis of
zeolite analogues, Nature 430 (2004) 10121016.
[6] E.R. Parnham, E.A. Drylie, P.S. Wheatley, A.M.Z. Slawin, R.E. Morris, Ionothermal
materials synthesis using unstable deep-eutectic solvents as template-delivery
agents, Angew. Chem. Int. Ed. 45 (2006) 49624966.
[7] C.P. Tsao, C.Y. Sheu, N. Nguyen, K.H. Lii, Ionothermal synthesis of
metal oxalatophosphonates with a three-dimensional framework structure: Na2 M3 (C2 O4 )3 (CH3 PO3 H)2 (M = FeII and MnII), Inorg. Chem. 45 (2006)
63616364.
[8] J.H. Liao, P.C. Wu, Y.H. Bai, Eutectic mixture of choline chloride/urea as a green
solvent in synthesis of a coordination polymer: [Zn(O3 PCH2 CO2 )]NH4 , Inorg.
Chem. Commun. 8 (2005) 390392.
[9] J. Zhang, T. Wu, S.M. Chen, P.Y. Feng, X.H. Bu, Versatile structure-directing roles
of deep-eutectic solvents and their implication in the generation of porosity and
open metal sites for gas storage, Angew. Chem. Int. Ed. 48 (2009) 34863490.
[10] H.G. Liao, Y.X. Jiang, Z.Y. Zhou, S.P. Chen, S.G. Sun, Shape-controlled
synthesis of gold nanoparticles in deep eutectic solvents for studies of
structurefunctionality relationships in electrocatalysis, Angew. Chem. Int. Ed.
47 (2008) 91009103.
[11] R.E. Morris, Ionothermal synthesisionic liquids as functional solvents in the
preparation of crystalline materials, Chem. Commun. (2009) 29902998.
[12] E.R. Parnham, R.E. Morris, Ionothermal synthesis of zeolites, metalorganic
frameworks, and inorganicorganic hybrids, Acc. Chem. Res. 40 (2007)
10051013.
[13] A. Fujishima, K. Honda, Electrochemical photolysis of water at a semiconductor
electrode, Nature 238 (1972) 3738.
[14] P.V. Kamat, R. Huehn, R. Nicolaescu, A sense and shoot approach for photocatalytic degradation of organic contaminants in water, J. Phys. Chem. B 106
(2002) 788794.
[15] J.G. Yu, L.J. Zhang, B. Cheng, Y.R. Su, Hydrothermal preparation and photocatalytic activity of hierarchically sponge-likemacro-/mesoporous titania, J. Phys.
Chem. C 111 (2007) 1058210589.

[16] A. Kudo, K. Omori, H. Kato, A novel aqueous process for preparation of crystal
form-controlled and highly crystalline BiVO4 powder from layered vanadates
at room temperature and its photocatalytic and photophysical properties, J.
Am. Chem. Soc. 121 (1999) 1145911467.
[17] T. Yang, D.G. Xia, Self-assembly of highly crystalline spherical BiVO4 in aqueous
solutions, J. Cryst. Growth 311 (2009) 45054509.
[18] L. Ge, Novel visible-light-driven Pt/BiVO4 photocatalyst for efcient degradation of methyl orange, J. Mol. Catal. A: Chem. 282 (2008) 6266.
[19] Y.F. Sun, C.Z. Wu, R. Long, Y. Cui, S.D. Zhang, Y. Xie, Synthetic loosely packed
monoclinic BiVO4 nanoellipsoids with novel multiresponses to visible light,
trace gas and temperature, Chem. Commun. (2009) 45424544.
[20] L. Zhou, W.Z. Wang, H.L. Xu, Controllable synthesis of three-dimensional welldened BiVO4 mesocrystals via a facile additive-free aqueous strategy, Cryst.
Growth Des. 8 (2008) 728733.
[21] S.S. Dunkle, R.J. Helmich, K.S. Suslick, BiVO4 as a visible-light photocatalyst prepared by ultrasonic spray pyrolysis, J. Phys. Chem. C 113 (2009) 1198011983.
[22] H.M. Zhang, J.B. Liu, H. Wang, W.X. Zhang, H. Yan, Rapid microwave-assisted
synthesis of phase controlled BiVO4 nanocrystals and research on photocatalytic properties under visible light irradiation, J. Nanopart. Res. 10 (2008)
767774.
[23] X.F. Zhang, Y.B. Zhang, X. Quan, S. Chen, Preparation of Ag doped BiVO4 lm and
its enhanced photoelectrocatalytic (PEC) ability of phenol degradation under
visible light, J. Hazard. Mater. 167 (2009) 911914.
[24] H.Q. Jiang, M. Nagai, K. Kobayashi, Enhanced photocatalytic activity for degradation of methylene blue over V2 O5 /BiVO4 composite, J. Alloys Compd. 479
(2009) 821827.
[25] M. Shang, W.Z. Wang, L. Zhou, S.M. Sun, W.Z. Yin, Nanosized BiVO4 with high
visible-light-induced photocatalytic activity: ultrasonic-assisted synthesis and
protective effect of surfactant, J. Hazard. Mater. 172 (2009) 338344.
[26] W.Z. Yin, W.Z. Wang, M. Shang, L. Zhou, S.M. Sun, L. Wang, BiVO4 hollow
nanospheres: anchoring synthesis, growth mechanism, and their application
in photocatalysis, Eur. J. Inorg. Chem. (2009) 43794384.
[27] L. Zhang, D.R. Chen, X.L. Jiao, Monoclinic structured BiVO4 nanosheets:
hydrothermal preparation, formation mechanism, and coloristic and photocatalytic properties, J. Phys. Chem. B 110 (2006) 26682673.
[28] L. Zhou, W.Z. Wang, L.S. Zhang, H.L. Xu, W. Zhu, Single-Crystalline BiVO4 microtubes with square cross-sections: microstructure, growth mechanism, and
photocatalytic property, J. Phys. Chem. C 111 (2007) 1365913664.
[29] L. Ren, L. Jin, J.B. Wang, F. Yang, M.Q. Qiu, Y. Yu, Template-free synthesis of
BiVO4 nanostructures: I. Nanotubes with hexagonal cross sections by oriented
attachment and their photocatalytic property for water splitting under visible
light, Nanotechnology 20 (2009) 115603115612.
S. Music,
M. Ivanda, M. S youfek,

Synthesis and characteri[30] M. Gotic,

S. Popovic,
sation of bismuth(III) vanadate, J. Mol. Struct. 744747 (2005) 535540.
[31] W. Liu, L.X. Cao, G. Su, H.S. Liu, X.F. Wang, L. Zhang, Ultrasound assisted synthesis
of monoclinic structured spindle BiVO4 particles with hollow structure and its
photocatalytic property, Ultrason. Sonochem. 17 (2010) 669674.
[32] M.N. Novokreshchenova, Y. Yukhin, B.B. Bokhonov, Highly pure bismuth (III)
oxochloride synthesis, Chem. Sust. Dev. 13 (2005) 563568.
[33] C. Zhang, J. Chen, X. Zhu, Y. Zhou, D. Li, Synthesis of tributylphosphate capped
luminescent rare earth phosphate nanocrystals in an ionic liquid microemulsion, Chem. Mater. 21 (2009) 35703575.
[34] H. Fu, C. Pan, W. Yao, Y. Zhu, Visible-light-induced degradation of rhodamine B
by nanosized Bi2 WO6 , J. Phys. Chem. B 109 (2005) 2243222439.
[35] D. Wang, J. Tang, Z. Zou, J. Ye, Photophysical and photocatalytic properties of
a new series of visible-light-driven photocatalysts M3 V2 O8 (M = Mg, Ni, Zn),
Chem. Mater. 17 (2005) 51775182.
[36] M. Oshikiri, M. Boero, J. Ye, Z. Zou, G. Kido, Electronic structure of promising
photocatalysts InMO4 (M = V, Nb, Ta) and BiVO4 for water decomposition in the
visible wavelength region, J. Chem. Phys. 117 (2002) 73137318.
[37] C. Zhang, Y. Zhu, Synthesis of square Bi2 WO6 nanoplates as high-activity visiblelight-driven photocatalysts, Chem. Mater. 17 (2005) 35373545.
[38] M.A. Butler, Photoelectrolysis and physical properties of the semiconducting
electrode WO2 , J. Appl. Phys. 48 (1977) 19141918.
[39] M. Long, W.M. Cai, J. Cai, B.X. Zhou, X.Y. Chai, Y.H. Wu, Efcient photocatalytic degradation of phenol over Co3 O4 /BiVO4 composite under visible light
irradiation, J. Phys. Chem. B 110 (2006) 2021120216.
[40] W. Zhao, C. Chen, X. Li, J. Zhao, Photodegradation of sulforhodamine-B dye
in platinized titania dispersions under visible light irradiation: inuence of
platinum as a functional co-catalyst, J. Phys. Chem. B 106 (2002) 5022
5028.