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由TiO2/Cu2O复合膜原位生成的芬顿试剂:可见光照射下利用TiO2的新方法。

In situ Fenton reagent generated from TiO2/Cu2O composite film: a new way to utilize TiO2 under visible light irradiation.

作者信息

Zhang Yong-Gang, Ma Li-Li, Li Jia-Lin, Yu Ying

机构信息

Institute of Nanoscience and Nanotechnology, HuaZhong Normal University, Wuhan 430079, People's Republic of China.

出版信息

Environ Sci Technol. 2007 Sep 1;41(17):6264-9. doi: 10.1021/es070345i.

Abstract

TiO2/Cu2O composite is prepared by a simple electrochemical method and coated on glass matrix through a spraying method. The obtained composite is characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect of TiO2/Cu2O composite films with different ratio of TiO2 and Cu2O on photodegradation of the dye methylene blue under visible light is investigated in detail. It is found that the photocatalytic activity of TiO2/Cu2O composite film with the presence of FeSO4 and EDTA is much higher than that for the similar system with only TiO2 and Cu2O film respectively. Without the presence of FeSO4 and EDTA, there is no degradation for methylene blue. The exploration of the optimized parameters for the degradation of methylene blue by using TiO2/Cu2O composite film as catalyst under visible light was also carried out. The most significant factor is the amount of Ti02 in the composite, and the second significant factor is the concentration of FeSO4. During the degradation of methylene blue under visible light, TiO2/Cu2O composite film generates H202, and Fenton regent is formed with Fe2+ and EDTA, which is detected in this study. The mechanism for the great improvement of photocatalytic activity of TiO2/Cu2O composite film under visible light is proposed by the valence band theory. Electrons excitated from TiO2/Cu2O composite under visible light are transferred from the conduction band of Cu2O to that of Ti02. The formed intermediate state of Ti 3+ ion is observed by X-ray photoelectron spectroscopy (XPS) on the TiO/Cu2O composite film. Additionally, the accumulated electrons in the conduction band of TiO2 are transferred to oxygen on the TiO2 surface for the formation of O2- or O2(2-), which combines with H+ to form H2O2. The evolved H202 with FeSO4 and EDTA forms Fenton reagentto degrade methylene blue. Compared to the traditional Fenton reagent, this new kind of in situ Fenton reagent generated from TiO2/Cu2O composite film does not need to supply H202. It is expected to be easily recycled, which may reduce second pollution and the cost of wastewater treatment. Moreover, this TiO/Cu2O composite film with FeSO4 and EDTA provides a new way to take advantage of TiO2 under visible light.

摘要

通过简单的电化学方法制备了TiO2/Cu2O复合材料,并通过喷涂法将其涂覆在玻璃基体上。采用X射线衍射(XRD)和扫描电子显微镜(SEM)对所得复合材料进行了表征。详细研究了不同TiO2与Cu2O比例的TiO2/Cu2O复合薄膜在可见光下对染料亚甲基蓝光降解的影响。结果发现,在FeSO4和EDTA存在下,TiO2/Cu2O复合薄膜的光催化活性分别远高于仅含TiO2和Cu2O薄膜的类似体系。在没有FeSO4和EDTA的情况下,亚甲基蓝没有降解。还对以TiO2/Cu2O复合薄膜为催化剂在可见光下降解亚甲基蓝的优化参数进行了探索。最显著的因素是复合材料中TiO2的含量,其次是FeSO4的浓度。在可见光下亚甲基蓝降解过程中,TiO2/Cu2O复合薄膜产生H2O2,并与Fe2+和EDTA形成芬顿试剂,本研究中对其进行了检测。利用价带理论提出了TiO2/Cu2O复合薄膜在可见光下光催化活性大幅提高的机理。在可见光下从TiO2/Cu2O复合材料激发的电子从Cu2O的导带转移到TiO2的导带。通过对TiO/Cu2O复合薄膜进行X射线光电子能谱(XPS)观察到形成的Ti 3+离子中间态。此外,TiO2导带中积累的电子转移到TiO2表面的氧上形成O2-或O2(2-),其与H+结合形成H2O2。生成的H2O2与FeSO4和EDTA形成芬顿试剂以降解亚甲基蓝。与传统芬顿试剂相比,这种由TiO2/Cu2O复合薄膜产生的新型原位芬顿试剂无需供应H2O2。预计其易于回收利用,这可能减少二次污染和废水处理成本。此外,这种含有FeSO4和EDTA的TiO/Cu2O复合薄膜为在可见光下利用TiO2提供了一种新途径。

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