负载型可见光光催化剂的制备及其光催化活性的研究
摘要
减小光催化剂的粒径是提高光催化剂活性的途径之一,但催化剂粒径减小到纳米尺度范围会发生聚集现象,将光催化剂负载到表面积较大的有孔材料上能有效避免光催化剂发生聚集,从而提高光催化活性。本研究工作重点集中在负载型可见光光催化剂的制备,合成方法的简化,对其存在形态的分析以及光催化活性提高的机理分析,主要包括以下两个方面的内容：
第一部分是分别在酸性条件和碱性条件下制备Cr-MCM-48,然后以Cr-MCM-48为载体,用浸渍法负载25%质量分数的Ti02,比较酸碱条件下制备的载体对TiO2/Cr-MCM-48光催化活性的影响。小角XRD分析表明,在所有的酸性条件下制备的样品中都有MCM-48介孔结构,但是碱性条件下制备的样品在Si/Cr小于20后介孔结构坍塌。广角XRD显示Ti02均呈无定形态。BET表明酸碱条件下制备的样品随着铬前驱体的增加表面积逐渐下降。UV-Vis DRS显示酸碱条件下制备的Cr-MCM-48和TiO2/Cr-MCM-48都有Cr6+存在,碱性条件下制备的所有样品都含有Cr3+,酸性条件下制备的样品在Si/Cr比小于20时开始出现多聚三价铬酸盐。以OrangeⅡ为降解目标物,对于在相同Si/Cr比条件下制得的样品,酸性体系制备的样品比碱性体系制备的样品具有更高的可见光催化活性,其中以样品aci-20-7-25 (Si/Cr=20, pH=7)的光催化活性最好,这主要是因为酸性条件下制备的样品中Cr6+物种含量较多。
第二部分是采用一步法首次将Bi2WO6负载于介孔MCM-48分子筛中。小角XRD、BET测试结果说明所制备得到的复合材料保持了MCM-48介孔分子筛的三维孔道结构。广角XRD、TEM测试结果表明钨酸铋纳米粒子高度分散于MCM-48中,粒子平均粒径随着金属前驱体浓度的增加而增大。UV-Vis DRS测试结果表明该复合体系在可见光区域有良好的吸收。Raman测试结果表明钨酸铋颗粒是以晶体的形态负载于MCM-48中。与传统的高温固态法和水热法相比,用一步法制备出来的Bi2WO6/MCM-48在适当的金属负载量的情况下,凭借较小的颗粒尺寸在可见光下表现出优越的活性。
A common approach to enhance the photocatalytic activity of potocatalyst is to reduce the particle size. These small particles tend to agglomerate by strong interparticle forces when the nanometric size region is reached. In order to avoid the aggregation of these small subnanometric clusters, one methodology that has been developed consists in incorporating these clusters inside the rigid framework of microporous hosts. In this thesis, supported visible-light-driven potocatalyst were synthesised and the performance was further investigated. The details are listed as follows:
1.Cr-MCM-48 was synthesized under acid condition and alkali condition and then 25 wt.% TiO2 were loaded by a post-impregnation method. XRD analysis showed that the MCM-48 structure was formed in all the samples synthesized under acid condition but only in the samples synthesized under alkali condition with Si/Cr ratio larger than 20. The BET surface area of TiO2/Cr-MCM-48 decreased with much more metals incorporated. DRS results indicated that Cr6+ was present in all samples. It was found that the photodegradation ability of 25% TiO2/Cr-MCM-48 synthesized under acid condition was higher than 25% TiO2/Cr-MCM-48 synthesized under alkali condition with the same Si/Cr ratio. This could be attributed to the presence of the high amount of Cr6+ in 25% TiO2/Cr-MCM-48 synthesized under acid condition. The sample aci-20-7-25 (Si/Cr=20, pH=7) showed the best visible-light photoactivity.
2. MCM-48 modified by Bi2WO6 with a high photocatalytic activity in the visible-light range was synthesized for the first time using a facile one-step process. The XRD patterns and Nitrogen adsorption isotherms of the prapared materials exhibited the characteristic of MCM-48. The XRD and TEM showed that the small subnanometric Bi2WO6 clusters began to aggregate into bigger Bi2WO6 particles when much more metal precursors were introduced. A blue shift in the band gap transition could be seen for Bi2WO6/MCM-48 in diffuse reflectance UV-vis spectra. Raman spectra illustrated the crystal structure of Bi2WO6 on MCM-48. In comparison to Bi2WO6 synthesised via traditional solid-state reactions and hydrothermal processes, the Bi2WO6/MCM-48 with small crystal size and appropriate metal oxide loading amount offers highly enhanced photocatalytic activity under visible light irradiation.
第一部分是分别在酸性条件和碱性条件下制备Cr-MCM-48,然后以Cr-MCM-48为载体,用浸渍法负载25%质量分数的Ti02,比较酸碱条件下制备的载体对TiO2/Cr-MCM-48光催化活性的影响。小角XRD分析表明,在所有的酸性条件下制备的样品中都有MCM-48介孔结构,但是碱性条件下制备的样品在Si/Cr小于20后介孔结构坍塌。广角XRD显示Ti02均呈无定形态。BET表明酸碱条件下制备的样品随着铬前驱体的增加表面积逐渐下降。UV-Vis DRS显示酸碱条件下制备的Cr-MCM-48和TiO2/Cr-MCM-48都有Cr6+存在,碱性条件下制备的所有样品都含有Cr3+,酸性条件下制备的样品在Si/Cr比小于20时开始出现多聚三价铬酸盐。以OrangeⅡ为降解目标物,对于在相同Si/Cr比条件下制得的样品,酸性体系制备的样品比碱性体系制备的样品具有更高的可见光催化活性,其中以样品aci-20-7-25 (Si/Cr=20, pH=7)的光催化活性最好,这主要是因为酸性条件下制备的样品中Cr6+物种含量较多。
第二部分是采用一步法首次将Bi2WO6负载于介孔MCM-48分子筛中。小角XRD、BET测试结果说明所制备得到的复合材料保持了MCM-48介孔分子筛的三维孔道结构。广角XRD、TEM测试结果表明钨酸铋纳米粒子高度分散于MCM-48中,粒子平均粒径随着金属前驱体浓度的增加而增大。UV-Vis DRS测试结果表明该复合体系在可见光区域有良好的吸收。Raman测试结果表明钨酸铋颗粒是以晶体的形态负载于MCM-48中。与传统的高温固态法和水热法相比,用一步法制备出来的Bi2WO6/MCM-48在适当的金属负载量的情况下,凭借较小的颗粒尺寸在可见光下表现出优越的活性。
A common approach to enhance the photocatalytic activity of potocatalyst is to reduce the particle size. These small particles tend to agglomerate by strong interparticle forces when the nanometric size region is reached. In order to avoid the aggregation of these small subnanometric clusters, one methodology that has been developed consists in incorporating these clusters inside the rigid framework of microporous hosts. In this thesis, supported visible-light-driven potocatalyst were synthesised and the performance was further investigated. The details are listed as follows:
1.Cr-MCM-48 was synthesized under acid condition and alkali condition and then 25 wt.% TiO2 were loaded by a post-impregnation method. XRD analysis showed that the MCM-48 structure was formed in all the samples synthesized under acid condition but only in the samples synthesized under alkali condition with Si/Cr ratio larger than 20. The BET surface area of TiO2/Cr-MCM-48 decreased with much more metals incorporated. DRS results indicated that Cr6+ was present in all samples. It was found that the photodegradation ability of 25% TiO2/Cr-MCM-48 synthesized under acid condition was higher than 25% TiO2/Cr-MCM-48 synthesized under alkali condition with the same Si/Cr ratio. This could be attributed to the presence of the high amount of Cr6+ in 25% TiO2/Cr-MCM-48 synthesized under acid condition. The sample aci-20-7-25 (Si/Cr=20, pH=7) showed the best visible-light photoactivity.
2. MCM-48 modified by Bi2WO6 with a high photocatalytic activity in the visible-light range was synthesized for the first time using a facile one-step process. The XRD patterns and Nitrogen adsorption isotherms of the prapared materials exhibited the characteristic of MCM-48. The XRD and TEM showed that the small subnanometric Bi2WO6 clusters began to aggregate into bigger Bi2WO6 particles when much more metal precursors were introduced. A blue shift in the band gap transition could be seen for Bi2WO6/MCM-48 in diffuse reflectance UV-vis spectra. Raman spectra illustrated the crystal structure of Bi2WO6 on MCM-48. In comparison to Bi2WO6 synthesised via traditional solid-state reactions and hydrothermal processes, the Bi2WO6/MCM-48 with small crystal size and appropriate metal oxide loading amount offers highly enhanced photocatalytic activity under visible light irradiation.
引文
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