具有光增强芬顿活性的有序介孔Fe/TiO_2的制备（英文）
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摘要
Fenton反应能够无选择性地降解有机物,甚至能够处理一些不能被生物降解的污染物,其原理为过氧化氢(H_2O_2)和亚铁离子(Fe~(2+))在酸性溶液中生成具有强氧化性的羟基自由基(·OH),后者将有机物氧化分解.因此,Fenton反应在处理环境问题中占有重要地位.将光催化与Fenton反应结合,相比单独的Fenton反应可提高氧化矿化性能,大大加快反应速率,减少H_2O_2使用量,降低成本,拓宽反应pH范围,其协同作用主要体现在两方面:(1)光催化产生的电子加速Fe~(3+)转变成Fe~(2+),促进Fenton反应进行;(2)Fenton反应中的H_2O_2与光生电子反应降低了电子-空穴的复合率,从而提高光催化降解效率.由于协同作用的存在,污染物的降解效率大大增加.到目前为止,Fenton反应中催化剂的载体多为惰性多孔材料,如沸石、粘土、金属氧化物、介孔二氧化硅、多孔碳和sp2型石墨(石墨烯、氧化石墨烯、碳纳米管等)等具有较大比表面积的材料.通常,增加载体的表面积有利于活性位点的分散,但是大比表面积的载体材料会削弱铁催化剂组分之间的相互作用,导致催化剂稳定性差,循环利用几次后会增加铁浸出量.因此,寻求大比表面积和高稳定性的光催化材料依然是巨大的挑战.本文首次通过蒸发诱导自组装法成功制备了Fe离子修饰的有序介孔TiO_2(FT-X),并通过XRD、BET、TEM、XPS和UV-Vis等分析手段对催化剂的结构进行了表征,同时以光芬顿降解罗丹明B反应考察了pH、污染物浓度及载体(TiO_2)结构对催化性能的影响.结果表明,由于Fe离子修饰减小了TiO_2的禁带宽度,FT复合材料具有更宽的可见光响应距离和更强的可见光吸收,在光芬顿反应过程中可以迅速转移电子,避免电子-空穴对的重组,同时加速了Fe~(3+)和Fe~(2+)的转化,显著提高了催化剂的催化性能.另外,将Fe离子原位锚定在有序介孔TiO_2的孔壁上,使FT具有规整的孔道结构和高的比表面积.与不规则多孔材料相比,一方面,该结构有利于活性位点的暴露,另一方面,有序的孔道更有利于光吸收和溶质传输.同时,Fe离子与载体之间具有较强的相互作用,可以有效地抑制反应过程中Fe离子的流失,FT-1.5样品(Fe:Ti摩尔比为1.5%)在经过5次循环测试后依然保持较高的催化活性.
Ordered mesoporous Fe/TiO_2 was prepared by an evaporation-induced self-assembly method.The iron ions were in situ embedded in the pore wall of the TiO_2 framework.The catalyst has excellent light-assisted Fenton catalytic performance under UV and visible light irradiation.X-ray diffraction and transmission electron microscopy results showed that the TiO_2 samples have an ordered two-dimensional hexagonal pore structure and an anatase phase structure with high crystallinity.The ordered pore structure of the TiO_2 photocatalyst with a large specific surface area is beneficial to mass transfer and light harvesting.Furthermore,iron ions can be controlled by embedding them into the TiO_2 framework to prevent iron ion loss and inactivation.After five cycles,the reaction rate of the ordered mesoporous Fe/TiO_2 remained unchanged,indicating that the material has stable performance and broad application prospects for the purification of environmental pollutants.
Ordered mesoporous Fe/TiO_2 was prepared by an evaporation-induced self-assembly method.The iron ions were in situ embedded in the pore wall of the TiO_2 framework.The catalyst has excellent light-assisted Fenton catalytic performance under UV and visible light irradiation.X-ray diffraction and transmission electron microscopy results showed that the TiO_2 samples have an ordered two-dimensional hexagonal pore structure and an anatase phase structure with high crystallinity.The ordered pore structure of the TiO_2 photocatalyst with a large specific surface area is beneficial to mass transfer and light harvesting.Furthermore,iron ions can be controlled by embedding them into the TiO_2 framework to prevent iron ion loss and inactivation.After five cycles,the reaction rate of the ordered mesoporous Fe/TiO_2 remained unchanged,indicating that the material has stable performance and broad application prospects for the purification of environmental pollutants.
引文
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