Morphology and Photoluminescence of Ba0.5Sr0.5MoO4 Powders by a Molten Salt Method
Ba0.5Sr0.5MoO4 powders with scheelite-type tetragonal structure were successfully synthesized by a molten salt method. The structure, morphology, and luminescent property of the as-prepared powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL), respectively. The results show that the tetragonal Ba0.5Sr0.5MoO4 powders were synthesized at 650°C for 6 h by the molten salt method. The calcining temperature, the soaking time, and the molar ratio of the salt to Na2MoO4 have great influence on the phase, size, morphology, and PL properties. The better crystallinity and smaller particle size, the higher PL emission peak is.
The fabrication of nano- to microscale inorganic materials with special size and morphology is of great interest for the study of material chemistry because of the importance in basic scientific research and potential technology applications of such materials [1, 2]. In recent years, molybdates and tungstates have attracted the interest of many technological fields and scientific areas owing to their wide potential application, including solid-state lasers , optic fiber , stimulated Raman scatters , catalysts , and microwave applications .
The molybdates with scheelite-type tetragonal structure are characterized by the general formula ABO4 (A = Ca, Sr, Ba, Pb; B = Mo), space group I41/a, and symmetry [8, 9]. These materials have been prepared in both powder and film forms by means of several technologies, such as electrochemical method , hydrothermal , solid-state reaction , and sol-gel method . However, these approaches still have some limitations, for example, the as-prepared samples are not only irregular in morphology and large in particle size, but also of small production and high cost.
Recently, researchers mostly pay attention to unit material systems and binary or multivariate molybdate thin films. Pôrto et al.  investigated the structure and photoluminescence of CaxSr1−xWO4 system at room temperature by a soft chemical method and heat treated between 400°C and 700°C. Rangappa et al.  studied fabrication of Ba-rich crystalline Ba1−xSrxWO4 and Ba1−xCaxWO4 films at room temperature by mechanically assisted solution reaction. Shi et al.  synthesized Ca0.5Sr0.5MoO4: Eu3+ powder using a sol-gel method. Fewer researchers on improving the luminescent property of solid-solution powders were reported. In order to fully research their properties, the study of alkaline earth molybdate materials is necessary.
Molten salts are widely used as an effective chemical reaction medium to produce a high-temperature liquid environment for crystal growth. The ionic fluxes molten salts possess high reactivity toward different inorganic species and relatively low melting points which makes them convenient for preparation of inorganic materials. Molten salt method has advantages of simple instrumentation and easy manipulation. And it is environmentally friendly and available to a large-scale production. In this paper, we report on the synthesis of Ba0.5Sr0.5MoO4 with perfect crystalline morphology and homogeneous chemical composition by a molten salt method. Different synthesis parameters were discussed, and a possible crystallization was proposed. Finally, the luminescent properties of Ba0.5Sr0.5MoO4 under different soaking times were investigated.
Na2MoO4, BaCl2, and SrCl2 of analytic reagent grade were used as the raw materials. The molar ratio of Na2MoO4, BaCl2, and SrCl2 was 2 : 1 : 1, While the molar ratio of the KCl salt to Na2MoO4 was selected as 1 : 1, 3 : 1 and 6 : 1, respectively. Then, the mixture was ground well with absolute ethanol for 6 h. After drying at 80°C for 24 h in air, the mixture was calcined at 600°C~800°C for 1 h~8 h. Finally, the products were thoroughly washed with distilled water for several times and then dried at 80°C.
The crystallographic characterization of the products was investigated by X-ray diffractometer with Cu Kα radiation at a scan speed of 5°/min in the 2θ range from 20° to 60°. The morphologies of the products were observed by a scanning electron microscope. Room temperature PL spectrum was recorded on FL3-221 fluorescence spectrometer excited with a Xe lamp as excited source.
3. Results and Discussion
The XRD patterns of the as-prepared products obtained at different calcining temperatures for 6 h with 3 : 1 molar ratio of the KCl salt to Na2MoO4 as shown in Figure 1. The XRD results reveal that the calcining temperature plays an important role in controlling the phase purity. It is obviously observed that the product obtained at 600°C is pure scheelite-type tetragonal phase Ba0.5Sr0.5MoO4 (JCPDS 30–0157), and no impurities could be detected. Increasing the calcining temperature to 650°C, the diffraction peaks become stronger and sharper, which suggests that elevating heating temperature would favor the crystallization. But with further increasing calcined temperature above 700°C (Figures 1(c) and 1(d)), the strength of the peaks decreases, and the diffraction peaks split. The split is ascribed to phase separation. According to the comparison of the interplanar distance, the separation phase is Ba0.25Sr0.75MoO4 (JCPDS 28–1207) and Ba0.75Sr0.25MoO4 because of the high temperature.
Figure 2 shows SEM images of the as-prepared products at different calcining temperatures for 6 h, with 3 : 1 molar ratio of the salt to Na2MoO4. It can be noted that when the reaction temperature keeps at 600°C, Ba0.5Sr0.5MoO4 powders have octahedron shape with inhomogeneous size. The size distribution of the particle is board. When the temperature increases to 650°C, the size distribution of the octahedrons narrows, and the mean size is 4.68 μm. With the increasing of temperature, abnormal particle growth is observed, and the mean size of the products increases to 6.50 μm. When the temperature further increases to 800°C, flake-like particles substitute the octahedrons gradually.
Figure 3 shows XRD patterns of the as-prepared products synthesized by the molten salt method at 650°C for 6 h, varying the molar ratio of the salt to Na2MoO4. It is obvious that the three XRD patterns are similar when the molar ratio is 1 : 1, 3 : 1 and 6 : 1, and all the patterns can be indexed to a pure tetragonal phase of Ba0.5Sr0.5MoO4. Further increasing the ratio of the molar ratio of the salt to the Na2MoO4 from 1 : 1 to 6 : 1 does not lead to obvious changes in the intensity and the width of the peaks.
During the molten salt synthesis process, the mass transfer process is related to the liquids formed by salt melting, so the size and morphology of the particles can be influenced by the content of the salts directly. The effect of the mole ratio of the salt to Na2MoO4 on Ba0.5Sr0.5MoO4 crystallizing morphology is shown in Figure 4. When the molar ratio is 1 : 1, the surface of the powders is irregular, and the size of the particles is board. When the molar ratio increased to 3 : 1 in Figure 2(b), homogeneous octahedrons with well-defined faces are obtained. When the molar ratio increases to 6 : 1, the dimension distribution of the particles broadens, and the edges of octahedrons turn vague. The reason is that with the increasing of salts, the content of the liquid phase increases gradually at high-temperature reaction system. The reaction changes from solid-state reaction to liquid phase reaction. At last, the liquid-phase reaction plays a dominant role. Thus, the size of particles decreases. When the content of salts is too much, redundant liquid phase is obtained, which depresses particle growth.
(a) 1 : 1
(b) 6 : 1
Figure 5 shows XRD patterns of the products obtained at 650°C for different soaking time, with 3 : 1 molar ratio of the salt to Na2MoO4. The XRD results reveal that the soaking time plays an important role in controlling the phase structures. When the soaking time is 1 h, only BaMoO4 peaks (JCPDS 08–0455) and other impurity Sr0.8Ba0.2CO3 phase peaks appear (Figure 5(a)). As the soaking time is prolonged to 2 h, no impurity phase peaks are detected and all of the diffraction peaks can be indexed to the scheelite-type tetragonal structure. The tetragonal phase of Ba0.5Sr0.5MoO4 remained when the soaking time is controlled in the range from 4 h to 8 h (Figures 5(c)–5(e)). In addition, the strong and sharp diffraction peaks indicate a good crystallinity of the products.
According to Donnay-Harker rules , as to tetragonal structure, the surface of faces is higher than that of faces. The high-energy faces have higher reactivity and growth rate, which makes faces shrink to disappear completely, so as to form octahedrons . It is reported that anions play a key role in morphology . In the growth process of Ba0.5Sr0.5MoO4, Chloride could preferentially and selectively adsorb on the and faces of Ba0.5Sr0.5MoO4. The faster growing rate along the directions than that along the directions facilitates the formation of octahedron morphology with exposed faces.
Figure 6 shows SEM images of the as-prepared products obtained at 650°C for different soaking times with 3 : 1 molar ratio of the salt to Na2MoO4. Figure 6(a) shows that micro-octahedrons are observed, and some micro-octahedrons self-assemble to big octahedrons along faces at 2 h. Figure 6(b) shows that when the soaking time is 4 h, inhomogeneous octahedrons are identified, and the mean size is 5.69 μm (Figure 7). When the soaking time is 6 h, the morphology of octahedrons is more uniform and well defined. The distribution of the particles also narrows. Eventually, when the soaking time is prolonged to 8 h, the distribution broadens.
(a) 2 h
(b) 4 h
(c) 8 h
Figure 8 shows the PL spectra of Ba0.5Sr0.5MoO4 powders obtained at 650°C for the holding time of 2 h~8 h, with 3 : 1 molar ratio of the salt to Na2MoO4. All Ba0.5Sr0.5MoO4 powders with different morphologies exhibited the same blue peaks around 460 nm using a 398 nm excitation line. Wu et al.  verified the blue emissions of molybdates, which were attributed to the 1T2 → 1T1 electronic transitions into the [MoO4] tetrahedron groups, which can be treated as excitons. Our results also indicate that with the increase of the soaking time from 2 h to 8 h, the intensity of the diffraction peaks increases gradually (Figure 5). And the mean particle size is 3.18 μm, 5.69 μm, 4.68 μm, and 6.20 μm, respectively (Figure 7). According to Figure 8, when the soaking time is 6 h, the luminescence of the particles is the best. Therefore, the better crystallinity and smaller particle size, the higher PL emission. The same conclusion has been reported before .
In this paper, Ba0.5Sr0.5MoO4 powders with octahedrons can be synthesized by a molten salt method at 650°C for 6 h. The particle size, morphology, and crystallinity of Ba0.5Sr0.5MoO4 crystallites depend on the reaction temperature, the holding time, and the molar ratio of KCl to the Na2MoO4. The PL properties are strongly dependent on their particle size and crystallinity. The better crystallinity and smaller particle size, the higher PL emission peak.
The authors acknowledge the financial support from Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions.
A. P. Alivisatos, “Semiconductor clusters, nanocrystals, and quantum dots,” Science, vol. 271, no. 5251, pp. 933–937, 1996.View at: Google Scholar
D. D. Archibald and S. Mann, “Template mineralization of self-assembled anisotropic lipid microstructures,” Nature, vol. 364, no. 6436, pp. 430–433, 1993.View at: Google Scholar
V. A. Morozov, A. V. Arakcheeva, G. Chapuis, N. Guiblin, M. D. Rossell, and G. Van Tendeloo, “KNd(MoO4)2: a new incommensurate modulated structure in the scheelite family,” Chemistry of Materials, vol. 18, no. 17, pp. 4075–4082, 2006.View at: Publisher Site | Google Scholar
Y. Zhang, F. Yang, J. Yang, Y. Tang, and P. Yuan, “Synthesis of crystalline SrMoO4 nanowires from polyoxometalates,” Solid State Communications, vol. 133, no. 12, pp. 759–763, 2005.View at: Publisher Site | Google Scholar
Z. C. Ling, H. R. Xia, D. G. Ran et al., “Lattice vibration spectra and thermal properties of SrWO4 single crystal,” Chemical Physics Letters, vol. 426, no. 1–3, pp. 85–90, 2006.View at: Publisher Site | Google Scholar
J. Bi, L. Wu, Y. Zhang, Z. Li, J. Li, and X. Fu, “Solvothermal preparation, electronic structure and photocatalytic properties of PbMoO4 and SrMoO4,” Applied Catalysis B, vol. 91, no. 1-2, pp. 135–143, 2009.View at: Publisher Site | Google Scholar
R. C. Pullar, S. Farrah, and N. M. Alford, “MgWO4, ZnWO4, NiWO4 and CoWO4 microwave dielectric ceramics,” Journal of the European Ceramic Society, vol. 27, no. 2-3, pp. 1059–1063, 2007.View at: Publisher Site | Google Scholar
M. Tyagi, Sangeeta, D. G. Desai, and S. C. Sabharwal, “New observations on the luminescence of lead molybdate crystals,” Journal of Luminescence, vol. 128, no. 1, pp. 22–26, 2008.View at: Publisher Site | Google Scholar
T. Thongtem, S. Kaowphong, and S. Thongtem, “Influence of cetyltrimethylammonium bromide on the morphology of AWO4 (A = Ca, Sr) prepared by cyclic microwave irradiation,” Applied Surface Science, vol. 254, no. 23, pp. 7765–7769, 2008.View at: Publisher Site | Google Scholar
W. S. Cho and M. Yoshimura, “Structural evolution and characterization of crystallized luminescent Sr1−xCaxWO4 solid-solution films prepared by an electrochemical method at room temperature,” Journal of Applied Physics, vol. 83, no. 1, pp. 518–523, 1998.View at: Google Scholar
Z. L. Fu, W. W. Xia, Q. S. Li, X. Y. Cui, and W. H. Li, “Highly uniform NaLa(MoO4)2: Ln3+(, Dy) microspheres: template-free hydrothermal synthesis, growing mechanism, and luminescent properties,” CrystEngComm, vol. 14, pp. 4618–4624, 2012.View at: Google Scholar
E. Tomaszewicz, S. M. Kaczmarek, and H. Fuks, “New cadmium and rare-earth metal molybdates with scheelite-type structure,” Materials Chemistry and Physics, vol. 122, no. 2-3, pp. 595–601, 2010.View at: Publisher Site | Google Scholar
A. Kaddouri, E. Tempesti, and C. Mazzocchia, “Comparative study of β-nickel molybdate phase obtained by conventional precipitation and the sol-gel method,” Materials Research Bulletin, vol. 39, no. 4-5, pp. 695–706, 2004.View at: Publisher Site | Google Scholar
S. L. Pôrto, E. Longo, P. S. Pizani et al., “Photoluminescence in the CaxSr1−xWO4 system at room temperature,” Journal of Solid State Chemistry, vol. 181, no. 8, pp. 1876–1881, 2008.View at: Publisher Site | Google Scholar
D. Rangappa, T. Fujiwara, T. Watanabe, and M. Yoshimura, “Preparation of Ba1−xSrxWO4 and Ba1−xCaxWO4 films on tungsten plate by mechanically assisted solution reaction at room temperature,” Materials Chemistry and Physics, vol. 109, no. 2-3, pp. 217–223, 2008.View at: Publisher Site | Google Scholar
W. Shi, J. Chen, and S. Gao, “Preparation and characterization of red-luminescence phosphors Ca0.5Sr0.5MoO4:EU3+ for white-light-emitting diodes,” Journal of the Chinese Ceramic Society, vol. 39, no. 2, pp. 219–222, 2011.View at: Google Scholar
J. D. H. Donnay and D. Harker, “A new law of crystal morphology extending the law of bravais,” Journal of Mineralogical Society of American, vol. 22, pp. 446–467, 1937.View at: Google Scholar
T. He, D. Chen, X. Jiao, and Y. Wang, “Co3O4 nanoboxes: surfactant-templated fabrication and microstructure characterization,” Advanced Materials, vol. 18, no. 8, pp. 1078–1082, 2006.View at: Publisher Site | Google Scholar
L. Gao, X. Ge, Z. Chai, G. Xu, X. Wang, and C. Wang, “Shape-controlled synthesis of octahedral α-NaYF4 and its rare earth doped submicrometer particles in acetic acid,” Nano Research, vol. 2, no. 7, pp. 565–574, 2009.View at: Publisher Site | Google Scholar
X. Wu, J. Du, H. Li et al., “Aqueous mineralization process to synthesize uniform shuttle-like BaMoO4 microcrystals at room temperature,” Journal of Solid State Chemistry, vol. 180, no. 11, pp. 3288–3295, 2007.View at: Publisher Site | Google Scholar
Y. Wang, J. Ma, J. Tao et al., “Low temperature synthesis of CaMoO4 nanoparticles,” Ceramics International, vol. 33, no. 4, pp. 693–695, 2007.View at: Publisher Site | Google Scholar