Preparation of photocatalytic materials MIL-125(Ti)/BiOI and photocatalytic performance study
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摘要: 以五水硝酸铋、碘化钾、MIL-125（Ti）为原料，以乙二醇为溶剂，以柠檬酸为结构诱导剂，通过一步共沉淀法制备了异质结结构光催化剂MIL-125（Ti）/BiOI，并测试了该催化剂在可见光下对有机染料罗丹明B的光催化降解效果.通过XRD（X-ray Diffraction）、PL（Photolumiscence）、SEM（Scanning Electron Microscope）、BET和UV-Vis（Ultraviolet and Visible Spectrophotometer）等表征手段研究了其结构、形貌、光谱与催化性能间的关系，并从能带结构上分析了其催化机理.结果表明，通过调节Ti：Bi，MIL-125（Ti）/BiOI在可见光照射下对有机染料罗丹明B有很好的光催化降解效果，并且该催化剂具有良好的稳定性，具有一定的工业化应用前景.
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关键词:
- MIL-125(Ti) /
- BiOI /
- 可见光 /
- 罗丹明B /
- 光催化降解
Abstract: With pentahydrate bismuth nitrate (Bi(NO3)35H2O), potassium iodide (KI), and MIL-125(Ti) as raw materials, ethylene glycol as solvent, and citric acid as the structural inducer, heterojunction structure light catalyst MIL-125(Ti)/BiOI was prepared through one-step coprecipitation. The effect of photocatalytic degradation of Rhodamine B in visible light was also tested. By a series of measurements, including XRD, PL, SEM, BET and UV-Vis, we researched the relationships between structure, morphology, spectrum and the catalytic performance of the catalyst. Furthermore, the catalytic mechanism was analysized via energy band structure. The results indicated that by adjusting the ratio of Ti/Bi, MIL-125(Ti)/BiOI has a good degradation effect on Rhodamine B under visible light radiation, which is stable and can be applied to industrial applications.-
Key words:
- MIL-125(Ti) /
- BiOI /
- visible light /
- Rhodamine B /
- photocatalytic degradation
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图 1 MIL-125(Ti)、BiOI和M-BiOI-$X$的XRD图
Fig. 1 XRD patterns of MIL-125(Ti), BiOI, and M-BiOI-$X$
图 2 DMF、MIL-125(Ti)的DMF溶液和MIL-125(Ti)/Bi(NO$_{3})_{3}$的DMF溶液的PL图谱
Fig. 2 PL spectrums of DMF, MIL-125(Ti)/DMF solution, and MIL-125(Ti)/Bi(NO$_{3})_{3}$ DMF solution
图 3 M-BiOI-1 (a)、M-BiOI-2 (b)、M-BiOI-3 (c)、M-BiOI-4 (d)、M-BiOI-5 (e)、M-BiOI-6 (f)的SEM照片
Fig. 3 SEM images of M-BiOI-1 (a), M-BiOI-2 (b), M-BiOI-3 (c), M-BiOI-4 (d), M-BiOI-5 (e), M-BiOI-6 (f)
图 7 MIL-125(Ti)、BiOI和M-BiOI-$X$样品对应的能带图
Fig. 7 Energy band diagram of MIL-125(Ti), BiOI, and M-BiOI-$X$
图 4 4 M-BiOI-5的EDX(a)以及各元素的元素映射图像(b)-(f)
Fig. 4 (a) EDX spectrum, (b)-(f) corresponding elemental mapping images of M-BiOI-5
图 5 BiOI、MIL-125 (Ti)和M-BiOI-$X$的N$_{2}$吸附-脱附等温线
Fig. 5 N$_{2}$ absorption-desorption isotherm spectrums of BiOI, MIL-125 (Ti), and M-BiOI-$X$
图 8 MIL-125(Ti)、BiOI和M-BiOI-$X$样品对罗丹明B的光催化降解曲线
Fig. 8 Photocatalytic degradation of Rhodamine B by MIL-125 (Ti), BiOI, and M-BiOI-$X$
图 6 MIL-125(Ti)、BiOI和M-BiOI-$X$的UV-Vis漫反射光谱
Fig. 6 UV-Vis diffuse reflection spectrums of MIL-125(Ti), BiOI, and M-BiOI-$X$
图 9 MIL-125(Ti)、BiOI和M-BiOI-$X$样品降解的动力学线性拟合ln($C_{0}/C)\sim t$曲线
Fig. 9 Dynamic linear fitting curve ln($C_{0}/C)\sim t$ for MIL-125(Ti), BiOI, and M-BiOI-$X$
图 10 M-BiOI-5光催化性能测试前和测试后的XRD图
Fig. 10 XRD patternsof M-BiOI-5 before and after photocatalytic performance testing
图 11 可见光条件下M-BiOI-53次循环降解罗丹明B的降解曲线图比较
Fig. 11 Degradation curve for three cycles of degrading RhB for M-BiOI-5 under visible light
图 12 MIL-125(Ti)/BiOI异质结结构光催化剂机理图
Fig. 12 Mechanism of photocatalyst of heterostructure for MIL-125(Ti)/BiOI
表 1 BiOI、MIL-125 (Ti)和M-BiOI-$X$的比表面积、总孔体积、微孔体积
Tab. 1 Specific surface area, total pore volume, and micropore volume of BiOI,
样品 比表面积/(m$^{2}\cdot$g$^{-1}$) 总孔体积/(cm$^{3}\cdot$g$^{-1}$) 微孔体积/(cm$^{3}\cdot$g$^{-1}$) BiOI 13 0.101 0.121 M-BiOI-1 121 0.135 0.124 M-BiOI-2 297 0.326 0.236 M-BiOI-3 401 0.387 0.262 M-BiOI-4 506 0.432 0.298 M-BiOI-5 598 0.421 0.324 M-BiOI-6 768 0.413 0.376 MIL-125(Ti) 851 0.408 0.408 
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表 2 MIL-125(Ti)、BiOI和M-BiOI-$X$样品降解的动力学反应速率常数
Tab. 2 Kinetic reaction rate constant for MIL-125(Ti), BiOI, and M-BiOI-$X$
$k_{\rm app}$/min$^{-1}$ 样品 0.0066 BiOI 0.0099 M-BiOI-1 0.0112 M-BiOI-2 0.0134 M-BiOI-3 0.0303 M-BiOI-4 0.0316 M-BiOI-5 0.0153 M-BiOI-6 0.0091 MIL-125
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