Microstructure and properties of Fe2(MoO4)3 prepared by sintering recovery products from waste MoSi2
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摘要:
采用热蒸发法回收废旧MoSi2氧化煅烧产物MoO3，以回收MoO3粉末与Fe2O3为原料，经反应烧结制备Fe2(MoO4)3。讨论了MoSi2完全氧化所需的时间和温度，并研究了Fe2(MoO4)3材料的组织形貌、线收缩率、体积密度和光谱学性能。结果表明：废旧MoSi2材料粉末经500 ℃煅烧120 min以上时间即可完全氧化。在MoO3与Fe2O3反应烧结过程中，烧结温度越高，MoO3与Fe2O3反应越完全，所制备的Fe2(MoO4)3材料空隙随之增多，线收缩率升高，体积密度降低。与纯Fe2(MoO4)3材料相比，Fe2(MoO4)3和MoO3复合相的光生电子–空穴对更不易复合，理论光催化活性更高。以亚甲基蓝为染料，纯Fe2(MoO4)3对其具有良好的吸附性能，而Fe2(MoO4)3和MoO3复合相则表现出优异的光催化性能，且Fe2(MoO4)3和MoO3复合相的光催化降解循环稳定性最好。
Abstract:MoO3 was recovered from waste MoSi2 after oxidation roasting by thermal evaporation method, and Fe2(MoO4)3 was prepared by reaction sintering method using the recovered MoO3 and Fe2O3 as raw materials. The time and temperature for the complete oxidation of MoSi2 were discussed, and the microstructure, linear shrinkage, volume density, spectral properties of the prepared Fe2(MoO4)3 materials were studied. The results show that, the waste MoSi2 powders can be completely oxidized after calcination at 500 ℃ for more than 120 min. During the reaction sintering process of MoO3 and Fe2O3, the higher the sintering temperature, the more complete the reaction between MoO3 and Fe2O3; the void of the prepared Fe2(MoO4)3 materials increases, the line shrinkage rate increases, and the volume density decreases. Fluorescence spectrum analysis shows that, the photogenerated electron-hole pairs of the Fe2(MoO4)3 and MoO3 composite materials are more difficult to be recombined than those of the pure Fe2(MoO4)3, showing the higher photocatalytic activity for the composites. Using methylene blue as dye, the pure Fe2(MoO4)3 has the good adsorption performance, while the Fe2(MoO4)3 and MoO3 composites show the excellent photocatalytic performance, and the mixture of Fe2(MoO4)3 and MoO3 composites has the best photocatalytic degradation cycle stability.
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图 1 热蒸发回收MoO3装置示意图
Figure 1. Schematic diagram of the thermal evaporation recovery MoO3 device
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图 2 反应烧结制备Fe2(MoO4)3实验示意图
Figure 2. Illustration of the Fe2(MoO4)3 fabrication process by reactive sintering
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图 3 废旧MoSi2粉末煅烧氧化180 min的X射线衍射图谱（a）和随煅烧温度变化的质量增加率（b）
Figure 3. XRD patterns (a) and mass increase rate (b) of the waste MoSi2 powders oxidized for 180 min with different calcination temperature
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图 4 废旧MoSi2粉末500 ℃煅烧氧化的X射线衍射图谱（a）和随煅烧氧化时间变化的质量增加率（b）
Figure 4. XRD patterns (a) and mass increase rate (b) of the waste MoSi2 powders oxidized at 500 ℃ with different calcination oxidation time
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图 5 反应烧结制备Fe2(MoO4)3产物的X射线衍射图谱
Figure 5. XRD patterns of the Fe2(MoO4)3 products prepared by reaction sintering
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图 6 不同烧结温度条件下Fe2(MoO4)3产物微观形貌：（a）600 ℃；（b）700 ℃；（c）800 ℃
Figure 6. Microstructures of the Fe2(MoO4)3 products sintered at different sintering temperatures: (a) 600 ℃; (b) 700 ℃; (c) 800 ℃
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图 7 600 ℃（a）和700 ℃（b）烧结温度下Fe2(MoO4)3产物以及A点（c）、B点（d）和C点（e）能谱分析
Figure 7. SEM images of the Fe2(MoO4)3 products at 600 ℃ (a) and 700 ℃ (b) and the corresponding EDS analysis at points A (c), B (d) and C (e)
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图 8 烧结温度对Fe2(MoO4)3产物线收缩率及体积密度的影响
Figure 8. Linear shrinkage and bulk density of the Fe2(MoO4)3 products at different sintering temperatures
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图 9 700 ℃样品Fe2(MoO4)3的X射线光电子能谱图：（a）宽扫图；（b）Fe 2p；（c）Mo 3d；（d）O 1s
Figure 9. XPS spectrums of the Fe2(MoO4)3 products: (a) wide sweep; (b) Fe 2p; (c) Mo 3d; (d) O 1s
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图 10 700 ℃和800 ℃烧结产物的紫外可见漫反射光谱（a）和禁带宽度（b）
Figure 10. UV-VIS diffuse reflectance spectra (a) and band gap (b) of the products sintered at 700 ℃ and 800 ℃
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图 11 不同烧结温度产物在365 nm激发波长下的荧光光谱
Figure 11. Fluorescence spectra of the products at different sintering temperatures at 365 nm excitation wavelength
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图 12 700 ℃烧结产物的光催化降解测试：（a）暗处理30 min吸附降解率及光照60 min光催化率；（b）催化剂添加量对染料光催化性能的影响；（c）催化稳定性测试
Figure 12. Photocatalytic degradation tests of the products sintered at 700 ℃: (a) adsorption degradation efficiency in dark for 30 min and photocatalytic efficiency for 60 min illumination; (b) effect of catalyst amount on the photocatalytic degradation of products; (c) catalytic stability test for 4 cycles
表 1 废旧MoSi2粉末中元素种类及含量（质量分数）
Table 1 Chemical composition of the waste MoSi2 powders
% Mo Si O W Al Rh Se Fe Mg 45.78 28.05 13.00 8.17 2.16 0.53 0.36 0.17 0.12 
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