Effect of acidity coefficient on the phase composition and morphology of MoO3 synthesized by hydrothermal method
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摘要:
为研究合成氧化钼的组织结构与控制条件的关系，以仲钼酸铵为钼源，在没有添加任何结构导向剂的情况下，通过简单的水热法制备了六方相三氧化钼（h-MoO3）微米棒和正交相三氧化钼（α-MoO3）纳米带。利用X射线衍射仪、扫描电镜和综合热分析对合成MoO3的物相和形貌进行了表征，研究了酸度系数与MoO3相变过程和形貌变化的关系，分析了相变机理。结果表明，控制水热合成的酸度系数可得到不同相结构和形貌的MoO3。酸度系数小于12.0时，得到h-MoO3；酸度系数超过12.0后，h-MoO3逐渐减少；酸度系数达到48.0时，h-MoO3完全消失，得到α-MoO3纯相。酸度系数超过48.0后，α-MoO3形貌从针状向带状转变，沿着c轴生长，长度不断增加，从而获得一维纳米材料。
Abstract:To study the relationship between the structure and the control conditions of molybdenum oxide synthesis, the hexagonal molybdenum trioxide (h-MoO3) microbars and the orthogonal molybdenum trioxide (α-MoO3) nanobelts were prepared by simple hydrothermal method using ammonium paramolybdate as the molybdenum source without any structure guide agent. The phase composition and morphology of the synthesized MoO3 were characterized by X-ray diffraction, scanning electron microscope, and the comprehensive thermal analysis. The relationship between the acidity coefficient and the MoO3 phase transformation and morphology change was studied, and the phase transformation mechanism was discussed. The results show that MoO3 with the different phase structures and morphologies can be obtained by controlling the acidity coefficient during the hydrothermal synthesis. h-MoO3 is obtained when the acidity coefficient is less than 12.0, and gradually converts to α-MoO3 in case that the acidity coefficient is more than 12.0; h-MoO3 gradually decreases, and when the acidity coefficient is 48.0, h-MoO3 completely disappears and α-MoO3 is obtained. After the acidity coefficient is more than 48.0, the morphology of α-MoO3 changes from microbar to nanobelt, which grows along the c axis with the increasing aspect ratio, thus obtaining the one-dimensional nanomaterials.
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Keywords:
- molybdenum trioxide /
- hydrothermal method /
- acidity coefficient /
- microbar /
- nanobelt
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图 2 低酸度系数产物扫描电子显微形貌：（a）酸度系数2.0；（b）酸度系数3.6；（c）酸度系数6.0
Figure 2. SEM images of the low acidity coefficient products: (a) acidity coefficient 2.0; (b) acidity coefficient 3.6; (c) acidity coefficient 6.0
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图 3 仲钼酸铵和酸度系数为2.0、3.6时产物的热重−示差扫描量热曲线:（a）仲钼酸铵；（b）酸度系数2.0；（c）酸度系数3.6
Figure 3. TGA−DSC curves of AHM and products at the acidity coefficient of 2.0 and 3.6: (a) AHM; (b) acidity coefficient 2.0; (c) acidity coefficient 3.6
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图 5 中酸度系数产物的扫描电子显微形貌：（a）酸度系数9.0；（b）酸度系数12.0；（c）酸度系数15.0；（d）酸度系数30.0
Figure 5. SEM images of the middle acidity coefficient products: (a) acidity coefficient 9.0; (b) acidity coefficient 12.0; (c) acidity coefficient 15.0; (d) acidity coefficient 30.0
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图 7 高酸度系数产物的扫描电子显微形貌：（a）酸度系数30.0；（b）酸度系数48.0；（c）酸度系数73.0；（d）酸度系数91.0
Figure 7. SEM images of the high acidity coefficient products: (a) acidity coefficient 30.0; (b) acidity coefficient 48.0; (c) acidity coefficient 73.0; (d) acidity coefficient 91.0
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图 8 酸度系数48.0产物的热重−示差扫描量热曲线
Figure 8. TGA−DSC curves of the products at the acidity coefficient of 48.0
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图 9 MoO3结构示意图：（a）α-MoO3；（b）h-MoO3
Figure 9. Structural diagram of MoO3: (a) α-MoO3; (b) h-MoO3
表 1 实验配比和酸度系数
Table 1 Experimental ratio and the acidity coefficient
编号 仲钼酸铵 / g HNO3 / mL 酸度系数 1 6.00 3.2 2.0 2 3.25 3.2 3.6 3 2.00 3.2 6.0 4 1.30 3.2 9.0 5 1.00 3.2 12.0 6 1.00 4.0 15.0 7 1.00 8.0 30.0 8 1.00 13.0 48.0 9 1.00 4.0（浓） 73.0 10 1.00 5.0（浓） 91.0 注：最后两组实验采用的是稀释前的浓硝酸。 
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