Kyung Hyunsook, Lee Jaesang, Choi Wonyong
School of Environmental Science and Engineering, Pohang University of Science and Technology, Pohang 790-784, Korea.
Environ Sci Technol. 2005 Apr 1;39(7):2376-82. doi: 10.1021/es0492788.
This study reports synergistic effects in the simultaneous conversion of dyes and heavy metal ions in aqueous TiO2/dye/metal ion systems (ternary components) under visible light (lambda > 420 nm). TiO2/Cr(VI)/Acid Orange 7 (AO7), TiO2/Cr(VI)/Rhodamine B (RhB), TiO2/Ag+/AO7, and TiO2/Ag+/RhB were chosen as test systems. Although dyes can be degraded in TiO2 suspensions under visible light, their removal rates were markedly enhanced in the presence of metal ions. Similarly, the reduction rates of metal ions in visible-light-illuminated TiO2 suspensions were negligible, but they were highly accelerated with dyes present. In particular, the synergistic effect in the ternary system of TiO2/Cr(VI)/AO7 was outstanding. The presence of dissolved oxygen increased the photoreduction rate of Cr(VI) despite the fact that Cr(VI) and O2 are competing electron acceptors. This is ascribed to in-situ photogenerated H2O2 from O2, which acts as a reductant of Cr(VI). RhB and Ag+ ions could be also converted simultaneously under visible light both in the presence and absence of TiO2. The visible-light-induced reduction of Ag+ did not occur at all in TiO2/Ag+ system, but it was enabled in both TiO2/Ag+/ RhB and TiO2/Ag+/AO7 to generate Ag particles. On the other hand, the binary systems of Cr(VI)/AO7, Ag+/AO7, and Ag+/RhB show significant visible-light activities for the conversion of both dye and metal ion. In this case, metal ions and dyes seem to form complexes that induce intracomplex electron transfers upon visible-light absorption. The Cr(VI)/RhB system, however, exhibited insignificant visible-light reactivity.
本研究报道了在可见光(λ>420nm)下,TiO₂/染料/金属离子体系(三元组分)中染料和重金属离子同时转化时的协同效应。选取TiO₂/Cr(VI)/酸性橙7(AO7)、TiO₂/Cr(VI)/罗丹明B(RhB)、TiO₂/Ag⁺/AO7和TiO₂/Ag⁺/RhB作为测试体系。尽管染料在可见光下可在TiO₂悬浮液中降解,但在金属离子存在时其去除率显著提高。同样,在可见光照射的TiO₂悬浮液中金属离子的还原率可忽略不计,但有染料存在时还原率会大幅加快。特别是,TiO₂/Cr(VI)/AO7三元体系中的协同效应非常显著。尽管Cr(VI)和O₂是竞争电子受体,但溶解氧的存在提高了Cr(VI)的光还原率。这归因于O₂原位光生H₂O₂,其作为Cr(VI)的还原剂。在有和没有TiO₂的情况下,RhB和Ag⁺离子在可见光下也能同时转化。在TiO₂/Ag⁺体系中根本不会发生可见光诱导的Ag⁺还原,但在TiO₂/Ag⁺/RhB和TiO₂/Ag⁺/AO7中都能实现以生成Ag颗粒。另一方面,Cr(VI)/AO7、Ag⁺/AO7和Ag⁺/RhB二元体系对染料和金属离子的转化均表现出显著的可见光活性。在这种情况下,金属离子和染料似乎形成了络合物,在吸收可见光时会引发络合物内的电子转移。然而,Cr(VI)/RhB体系的可见光反应活性不明显。