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Journal of Hazardous Materials 181 (2010) 1102–1108

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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
Bismuth vanadate
Deep eutectic solvent

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 reaction–crystallization 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) [5–9]. 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 [10–12].

∗ Corresponding author. Tel.: +86 532 66781690; fax: +86 532 66781332.
E-mail address: (W. Liu).
0304-3894/$ – see front matter © 2010 Elsevier B.V. All rights reserved.

Recently, the decomposition of harmful organic and inorganic pollutants using photosensitized semiconductors as catalysts
has attracted increasing attention [13–15]. 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 [16–25]. 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 [26–29].
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 firstly the production of visiblelight-driven BiVO4 spindly microtubes in the deep eutectic solvent

800 nm and a wall thickness of ca. b = 0. The sample was then dropped onto a copper grid coated with a holey carbon film and dried in air. The final light yellowish products were centrifuged. A 250 mL beaker was dried in an oven at 80 ◦ C for about 2 h to evaporate the water and Fig. 1. For comparison. and then the photocatalyst powder put into the RhB solution to form the homogenerous suspension by ultrasonic bath for 5 min. the dispersion was filtered to separate the photocatalyst particles. Transmission electron microscopy (TEM) observations were carried out on a JEOL JEM-2100 instrument with accelerating voltage 200 kV in bright-field and selected-area electron diffraction (SAED) modes. 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. No peaks for any other phases or impurities were detected. then cooled to room temperature before used. In this way.6457 nm (JCPDS No. 2a) shows that the product is well-defined microtubes with a length of 8–10 ␮m. Results and discussion 3.1. The SEM image (Fig. washed with deionized water and absolute ethanol for several times. After irradiation for a designated time. 100 nm. IR spectra were collected using a Digilab-FTS-80 spectrophotometer using pressed KBr pellets of the samples. The specimens used for TEM studies were dispersed in absolute ethanol by ultrasonic treatment. The autoclave was sealed and kept at 150 ◦ C for 15 h.15418 nm) radiation under 40 kV and 100 mA. The baseline correction was performed using a calibrated reference sample of barium sulfate. In the typical process.7300 nm and c = 0. The corresponding TEM image (Fig. The spindly microtubes were prepared through a simple ionothermal method. 2c) demonstrates that the BiVO4 particles are spindle in shape with dentate openings.W. / Journal of Hazardous Materials 181 (2010) 1102–1108 1103 of urea/choline chloride.7331 nm and c = 0. UV–vis diffuse reflectance spectroscopy (UV–vis-DRS) in the spectral range from 200 to 700 nm was performed with a Hitachi U-3010 UV–vis spectrometer. The light yellow aqueous solution obtained after continuous vigorous stirring for 30 min was transferred into a 15mL Teflonlined autoclave. 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. XRD pattern of spindly BiVO4 microtubes prepared by ionothermal treatment at 150 ◦ C for 15 h in the solvent of urea/choline chloride. Then 1 g water was added into the solution to adjust the viscosity of the DES. 2b) demonstrates that the individual tube exhibits a spindly shape with a side length of ca. 2. Photoluminescence spectra were measured by Fluorolog-3-P with 450 W Xe lamp. and the RhB concentration of the filtrate were monitored by checking the absorbance at 553 nm during the photo degradation process using the UV–vis spectrophotometer.2. which are resistant biodegradation and direct photolysis. bulk BiVO4 particles were also prepared by the traditional solid-state reaction (SSR-BiVO4 ) according to the previous literature [30]. Distilled water was used in all experiments. As shown in Fig. b = 0. and the beaker was covered with UV cutoff filter to completely remove any radiation below 400 nm and to ensure illumination by visible-light only. The morphology and microstructure of as-prepared BiVO4 particles were measured by the electron microscopy.7300 nm. 1. 48-0744). the hollow interior structure of products can also be depicted as the encapsulation of such four long columns in parallel. Bi(NO3 )3 ·5H2 O (48. 100 mL RhB aqueous solution with a concentration of 1 × 10−5 M was added into the beaker in each experiment. the opening of these microtubes presents the novel saw-toothed structure. in which particles with other morphologies cannot be observed. but limited information about the hollow interior structure of as-prepared samples can be obtained due to the large particle size .6462 nm. A 500 W Xe lamp (10 cm above the beaker) was used as the light source. The evaluation of photocatalytic activity of the prepared samples for the photocatalytic decolorization of RhB aqueous solution was performed at ambient temperature. which is seldom in other tube-shaped materials reported in previous literatures.7331 nm. The morphologies and microstructures of as-prepared samples were examined with scanning electron microscopy (SEM.2 g. Connected with tooth tip of two openings. Prior to irradiation. Interestingly. JSM-6700F) and equipped with an energy-dispersive X-ray spectroscope (EDS). Photocatalytic test Rhodamine B (RhB). the distinct grooves on the rough surface of tubes can be identified clearly and divide the tube into four long columns with sharp heads. 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. Experimental procedures were as follows: the weight of catalysts used in each experiment was kept 0. Experimental 2. 2. Synthesis of spindly BiVO4 microtubes All the chemicals in this study were used as received from Shanghai Chemical Regent Factory of China without further purification. After magnetic stirring to homogenous liquid. is a popular probe molecule in the heterogeneous photocatalysis reaction. which agrees with the reported values of a = 0.7 mg) were added into the above solution under magnetic stirring.3. 3. 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. Liu et al. The Brunauer–Emmett–Teller (BET) surface areas were estimated with the use of a Micromeritics ASAP2010 Analyzer. as reported in our previous studies [31]. Close observation of the samples (Fig. The composition and microstructure of asprepared products are investigated and their photocatalytic activity is also evaluated. and then dried at 80 ◦ C in air. which was filled with 80% of the total volume. 2. all the diffraction peaks can be readily indexed to a pure monoclinic scheelite phase BiVO4 of lattice constants a = 0.5 mg) and NH4 VO3 (11. one of the N-containing dyes. 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␣ ( = 0.1.

the peak intensity of BiOCl decreases obviously while a new broad peak at 2 = 28◦ appears (Fig. a detailed time course experiment was carried out.36:3.80%) reveals that the elemental composition of the spindly tubes is vanadium. As the time increases to 40 min. the XRD pattern of the products are nearly the same as that of the 10 h one except for a little intensity increasing (Fig. It can be seen from Fig. bismuth. 3. (a) IR spectrum of the precursor and IR spectra of samples after ionothermal treatment at 150 ◦ C for (b) 40 min.5◦ and 46. 12.1104 W. 3 shows the XRD patterns of time series samples. (b) Close observation of microtubes showing the hollow structure and wall thickness. 2. 10 h and 15 h were also measured (Fig. 3c). 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. (c) 1 h. 1 h. the diffraction peaks of monoclinic BiVO4 can be clearly observed at 2 = 18. 0. 3b). and the remaining ones at 2 = 32. 3e). which is very close to the Bi:V molar ratio (1:1) in monoclinic BiVO4 . (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. V. 4). After treated for 10 h. The selected-area electron diffraction (SAED) pattern (Fig. The BET surface area of spindly BiVO4 samples is estimated to be ca. 71. FT-IR absorption spectra of the precursor and the samples prepared after ionothermal treatment for 40 min.9◦ .06-0249). 3f). Liu et al. After 1 h. This indicates that the mixture phases of monoclinic BiVO4 and BiOCl are produced in the sample after treated for 1 h. which was much higher than that of the reference SSR-BiVO4 sample of ca. 2d) reveals the single-crystal nature of the BiVO4 spindly tubes. The spectrum of precursor demonstrates a weak absorption of (Bi–O) at Fig. 15.71%. 3. (e) 10 h and (f) 15 h. the peaks corresponding to monoclinic BiVO4 become more and more dominant. Formation of spindly BiVO4 microtubes . and oxygen with a molar ratio of Bi:V = 3.75 m2 /g. With the time is prolonged to 2 h. and the diffraction peaks corresponding to BiOCl disappear except for few tiny peaks (Fig. / Journal of Hazardous Materials 181 (2010) 1102–1108 Fig. Fig. (d) 10 h and (e) 15 h in DES solution. (a) Low magnification SEM image of as-obtained product. 3. (b) 40 min.50%. (c) 1 h. When the time increases to 15 h. Fig. XRD patterns of as-prepared BiVO4 powders at various treated time (a) precursors.38. Bi.7◦ are assigned to BiOCl (Fig. 4. To investigate the formation process of spindly BiVO4 microtubes.6◦ and 28. 3d). all crystal diffraction peaks can be indexed to be a pure monoclinic phase BiVO4 (Fig. The EDS analysis (the percent content of the elements (wt%): O. (d) 2 h. 3a that only few weak reflections of the precursors without ionothermal treatment can be identified and are assigned to bismuth oxychloride BiOCl (PDF-2 No.2. (c) TEM image for a single BiVO4 microtube.46 m2 /g.

The absorptions of 1 (VO4 ) and 3 (VO4 ) (at around 751 cm−1 ) can be attributed to the vanadium amorphous phase and the band at 1637 cm−1 may be assigned to the absorbed CO2 in the air [29]. (b) 40 min. Liu et al. possibly deriving from the overlapped nanosheets. When the reactive time is prolonged to 40 min. Mass transportation to the growing regions would lead to undersaturation in the central part of the growing faces of each seeds. the peaks assigned to the choline chloride disappear gradually with the increase of treated time. the product treated for 10 h consists almost of wholly spindly microtubes with saw-toothed opening. Close observation (Fig. No microspheres can be found except for a quantity of irregular fragments adsorbed on the surface of the tubes. the weak peaks of (CH2 ). it could not provide enough reactants for the growth of BiVO4 crystals. 5c. Finally. as the time is extended to 15 h. the nanosheet aggregates evolve into ball-like compact microspheres with a diameter of ca. which causes the formation of Fig. which is in agreement with the above XRD results. Fig. BiOCl. (e) 10 h and (f) 15 h. as a buffer. Then. 5b inset). 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. 5b). Based on above results. thereby controlling efficiently the BiVO4 concentration within the bulk solution. Therefore. while the peak for Bi–Cl gradually decrease. d) 1 h. 10 nm. 5e. avoids the direct reaction between Bi3+ and VO3 − in the solvents. Second. The insets images of (a) and (b) show the close observation of BiOCl aggregations. a few small square-shaped microtubes growing out from the conglomeration of microspheres can be observed clearly in Fig. The remaining peaks including the broad peak of (OH) at 3430 cm. 5. 5a inset). With prolonged ionothermal treatment. Due to the mediation effect of BiOCl. and the peak of (N+ –CH2 –) at 1400 cm−1 .W. In addition. the formation of BiOCl at the initial stage results in the heterogeneous nucleation points for monoclinic phase BiVO4 . First. 5a shows that the precursors are well-defined BiOCl nanosheets with a thickness of ca. the simultaneously nucleation and growth of large number of monoclinic phase BiVO4 seeds will greatly reduce the concentration of BiVO4 in the bulk solution. (CH3 ) and ı(CH3 ) at 2923. BiVO4 microtubes with a length up to ca. As seen from Fig. / Journal of Hazardous Materials 181 (2010) 1102–1108 around 529 cm−1 . Whereas the enhanced absorption bands of (N+ –CH2 –) and ı(CH3 ) are observed in the samples treated for 10 and 15 h. it is observed that the absorptions of 1 (VO4 ) and 3 (VO4 ) gradually increase in quantity. that can be interpreted as the presence of bismuth oxochloride [32]. 1105 800 nm (Fig. The products collected at different reaction time were observed by SEM. indicating that most of choline chloride molecules have been removed during the crystallization process of BiVO4 . 2856. 2958 and 1460 cm−1 . mainly correspond to choline chloride molecules [33]. (c. part of which intersect each other into a flower-like morphology (Fig. When the time increases to 1 h. vanadium amorphous phase and adsorbed organic molecules. 10 ␮m are formed (Fig. it is noticeable that BiOCl plays the crucial roles in forming the monoclinic BiVO4 microtubes. A large amount of small protuberances appear distinctly on the surface of these spheres (Fig. . the microtubes begin to grow longer. which may results from the oriented adsorption of a small amount of organic molecules on the surface of samples. Generally. Morphology evolution of as-prepared BiVO4 samples with the reaction time (a) precursors. 5f). the precursor can be considered as the mixture of BiOCl.

(d) TEM photo of the nanosheets and the corresponding SAED pattern. UV–vis diffuse reflectance spectra of spindly BiVO4 microtubes and SSRBiVO4 samples. . 7. The values estimated from the intercept of the tangents to the plots were 2. whereas the conduction band is composed of V 3d orbitals. In order to investigate the electronic structure of as-obtained spindly structure.48 and 2.35]. (c) Close observation of the surface of as-prepared samples treated for 10 h. 7. According to the equation ˛Ep = K(Ep − Eg )1/2 (where ˛ is the absorption coefficient. 7. (b) High magnification SEM image of the corresponding samples. square-shaped crystal nuclei with hollow interior structure. the spindly BiVO4 tubes have the strong absorption in UV and visible-light regions with the steep shape. Ep is the discrete photoenergy. K is a constant. 6. UV–vis absorption spectra were measured for the spindly microtubes and SSR-BiVO4 samples. This can be confirmed by the concave surfaces observed in the initial crystal nuclei of BiVO4 (Fig. The charge transfer upon photo-excitation is thus supposed to occur from Bi 6s and O 2p hybrid orbitals to V 3d orbitals [36]. 6d inset) reveals that these nanosheets crystallize in the form of monoclinic BiVO4 . / Journal of Hazardous Materials 181 (2010) 1102–1108 Fig. as shown in inset of Fig. photon energy (h). thereby giving rise to the rough surfaces and ragged edges of BiVO4 microtubes.1106 W. (a) Low magnification SEM image of samples treated for 10 h.44 eV for spindly BiVO4 tubes and SSR-BiVO4 . Interestingly. Unlike BiVO4 microtubes reported in previous literatures [28. Liu et al. With the rise of time. which possibly results from the inductive effect of organic molecules in the solution. Inset: plots of (˛h)2 vs.3. and Eg is the band gap energy) [38]. Bi 6s and O 2p orbitals. 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. 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. 10 nm is observed clearly in the corresponding TEM image (Fig. In the growth process of microtubes. respectively. The energy of the band gap of BiVO4 photocatalyst could be thus obtained from the plots of (˛h)2 versus photon energy (h). The growth mechanism of spindly BiVO4 . part of solvent molecular can absorb on the surface of BiVO4 microtubes and thereby induce the nucleation and growth of the nanosheets. 6a and b). 6d) and the selected-area electron diffraction pattern (Fig. The increase in the bandgap of the as-prepared BiVO4 spindly microtubes could be indicative of the possible quantum 3. the spindly shape of the microtubes is obtained in our case. Since the valence band (VB) of BiVO4 is composed of hybridized Fig. This is also supported by the above results of IR.6]. therefore.29]. The sheet nature of these fragments with the thick length of ca. can be ascribed to the coexist effect of the reaction–crystallization process controlled by BiOCl concentration and the nucleation-growth process of nanosheets induced by solvent molecules adsorbed on the surface of microtubes. This nucleation and further growth of nanosheets derives possibly from the inductive effect of solvent molecules attached on the surface of microtubes. 5d). however. 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. As shown in Fig. which indicates that the visible-light adsorption is due to the band–gap transition [37]. 6c) demonstrates that these nanosheets not only adsorb but also grow closely together with the wall of microtubes. high magnification SEM photo (Fig. it is worthy of noting the presentation of the irregular fragments on the external/internal surfaces of BiVO4 microtubes (Fig.

which is in good accordance with that in the literature [40]. UV–vis spectra taken over time during the photodegradation of RhB mediated by BiVO4 spindly particles versus SSR-BiVO4 . which allows for the more efficient transfer of electron–hole pairs. Notably. The degradation curves of RhB using spindly BiVO4 microtubes and SSR-BiVO4 as photocatalysts are shown in Fig. lots of surface defects and nanostructure on the surface of microtubes can effectively promote the separation efficiency of the electron–hole pairs. the particles with well crystallinity can decrease the defects inside the crystals. it is not surprising that the well-crystallized spindly microtube shows the highest photocatalytic activity among the prepared samples. For example. the samples with prolonged ionothermal treatment demonstrate the improved photocatalytic activity under visiblelight irradiation (Fig. the presence of both light illumination and BiVO4 catalysts is necessary for the efficient photocatalytic degradation of RhB aqueous solution. which can usually offer more active adsorption sites and photocatalytic reaction centers. After irradiation for 300 min. 4. Therefore. Fig. 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. 8. Therefore. In one respect. 10. In addition. in another respect. As-obtained product exhibits a . Monoclinic structured BiVO4 microtubes with a length of ca. the absorption blue-shifts from 552 to 498 nm in the presence of the prepared spindly BiVO4 . Hence. The blank experiment in the absence of catalysts demonstrates a poor self-degradation of RhB under the visiblelight irradiation. The results demonstrate that the BiVO4 spindly particles have superior photocatalytic activities compared with the SSR-BiVO4 materials. After adsorption/desorption equilibrium between RhB molecules and the samples. the hollow internal structure and the rough surface create large surface area. generated inside the crystal. Conclusions Fig. 10). the much-enhanced visible-light-responsive photocatalytic property of spindly BiVO4 microtubes could be ascribed to their special tubular structure Fig.4. 3. the photocatalytic efficiency 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. 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.W. and spindly BVO4 (b) (ex = 375 nm). which clearly indicates that the recombination between the hole and the electron is greatly inhibited [39]. thus improving their response to visible-light. the concentration of RhB do not change with increasing reaction time for every measurement using BiVO4 samples under dark conditions without light illumination. The rate of photodegradation by spindly BiVO4 microtubes (98% in 300 min) is much faster than that by SSR-BiVO4 (16%). Accompanying with the decrease of absorption of RhB/BiVO4 suspension during the photodegradation is the distinct blue-shift of its major absorption band. / Journal of Hazardous Materials 181 (2010) 1102–1108 1107 confinement effects resulting from the nanosized building blocks on the surface of spindly tubes. 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. 9. Generally. The inset image is the degradation curves of RhB without photocatalysts and using spindly BiVO4 microtubes and SSRBiVO4 as photocatalysts. 8 shows the comparison of PL spectra of SSR-BVO4 sample and spindly BVO4 sample with excitation wavelength of 375 nm. to the surface. indicating that RhB has being fully demethylated. it is indicated that the spindly BiVO4 could be used as more efficient photocatalyst compared to the SSR-BiVO4 catalysts. 10 ␮m have been successfully fabricated in the deep eutectic solvent of urea/choline chloride. while the highest rate of photodegradation (98%) is observed for the sample ionothermally synthesized for 15 h. indicating removal of ethyl groups one by one. Fig. 9 inset. 9 shows the UV–vis spectra taken over time during the photodegradation of RhB mediated by BiVO4 spindly particles versus SSR-BiVO4 . Fig. The room temperature photoluminescence (PL) spectra of SSR-BVO4 (a). while in the same time period no distinct blue-shift is observed for SSR-BiVO4 materials as catalyst. morphology. RhB concentration changes with irradiation time over BiVO4 catalysts ionothermally prepared for various time. The possible explanation is due to the improved crystallization performance of the samples with the prolonged treated time. Liu et al.

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