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镍离子在缺氧条件下 UV 光存在时对 Fe/TiO₂纳米复合材料耦合脱除三氯乙烯和 2,4-二氯苯酚中的协同作用。

Synergistic effect of nickel ions on the coupled dechlorination of trichloroethylene and 2,4-dichlorophenol by Fe/TiO₂ nanocomposites in the presence of UV light under anoxic conditions.

机构信息

Department of Biomedical Engineering and Environmental Sciences, National Tsing Hua University, 101, sec. 2, Kuang-Fu Road, Hsinchu 30013, Taiwan.

出版信息

Water Res. 2011 Aug;45(14):4198-210. doi: 10.1016/j.watres.2011.05.019. Epub 2011 Jun 1.

Abstract

The coupled removal of priority pollutants by nanocomposite materials has recently been receiving much attention. In this study, trichloroethylene (TCE) and 2,4-dichlorophenol (DCP) in aqueous solutions were simultaneously removed by Fe/TiO₂ nanocomposites under anoxic conditions in the presence of nickel ions and UV light at 365 nm. Both TCE and DCP were effectively dechlorinated by Fe/TiO₂ nanocomposites, and the pseudo-first-order rate constants (k(obs)) for TCE and DCP dechlorination were (1.39 ± 0.05)×10⁻² and (1.08 ± 0.05)×10⁻² h⁻¹, respectively, which were higher than that by nanoscale zerovalent iron alone. In addition, the k(obs) for DCP dechlorination was enhanced by a factor of 77 when Fe/TiO₂ was illuminated with UV light for 2 h. Hydrodechlorination was found to be the major reaction pathway for TCE dechlorination, while DCP could undergo reductive dechlorination or react with hydroxyl radicals to produce 1,4-benzoquinone and phenol. TCE was a stronger electron acceptor than DCP, which could inhibit the dechlorination efficiency and rate of DCP during simultaneous removal processes. The addition of nickel ions significantly enhanced the simultaneous photodechlorination efficiency of TCE and DCP under the illumination of UV light. The k(obs) values for DCP and TCE photodechlorination by Fe/TiO₂ in the presence of 20-100 μM Ni(II) were 30.4-136 and 13.2-192 times greater, respectively, when compared with those in the dark. Electron spin resonance analysis showed that the photo-generated electron-hole pairs could be effectively separated through Ni ions cycling, leading to the improvement of electron transfer efficiency of TCE and DCP by Fe/TiO₂.

摘要

纳米复合材料对优先污染物的耦合去除最近受到了广泛关注。在这项研究中,在缺氧条件下,三氯乙烯(TCE)和 2,4-二氯苯酚(DCP)在水溶液中同时被 Fe/TiO₂纳米复合材料去除,其中镍离子和 365nm 的 UV 光同时存在。TCE 和 DCP 都被 Fe/TiO₂纳米复合材料有效地脱氯,TCE 和 DCP 脱氯的拟一级速率常数(k(obs))分别为(1.39±0.05)×10⁻²和(1.08±0.05)×10⁻² h⁻¹,高于单独使用纳米零价铁的速率常数。此外,当 Fe/TiO₂用 UV 光照射 2 小时时,DCP 脱氯的 k(obs)提高了 77 倍。氢还原脱氯被发现是 TCE 脱氯的主要反应途径,而 DCP 可以进行还原脱氯或与羟基自由基反应生成 1,4-苯醌和苯酚。TCE 是比 DCP 更强的电子受体,这会抑制 DCP 在同时去除过程中的脱氯效率和速率。添加镍离子在 UV 光照射下显著提高了 TCE 和 DCP 的同时光脱氯效率。当存在 20-100 μM Ni(II)时,Fe/TiO₂ 对 DCP 和 TCE 的光脱氯的 k(obs)值分别比黑暗中提高了 30.4-136 倍和 13.2-192 倍。电子自旋共振分析表明,光生电子-空穴对可以通过 Ni 离子循环有效地分离,从而提高了 TCE 和 DCP 通过 Fe/TiO₂的电子转移效率。

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