College of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, PR China.
Environ Sci Technol. 2013 Jan 2;47(1):518-25. doi: 10.1021/es302935e. Epub 2012 Dec 18.
Direct evidence was first demonstrated for the oxidative degradation of decabromodiphenyl ether (BDE209) in aqueous TiO(2) dispersions under UV irradiation (λ > 340 nm). BDE209 was hardly debrominated over TiO(2) in UV-irradiated acetonitrile dispersions, but the addition of water into the dispersions greatly enhanced its photocatalytic oxidative debromination. The debromination efficiency of BDE209 as high as 95.6% was achieved in aqueous TiO(2) dispersions after 12 h of UV irradiation. The photocatalytic oxidation of BDE209 resulted in generation of aromatic ring-opening intermediates such as brominated dienoic acids, which were further degraded by prolonging UV irradiation time. The photocatalytic oxidative debromination of BDE209 was further confirmed by the observation that the BDE209 degradation in water-acetonitrile mixtures with different water contents was positively correlated with the formation of •OH radicals, but not photogenerated electrons. The use of water not only avoided the scavenging of reactive radicals by organic solvent but also enhanced the adsorption of BDE209 on the surface of TiO(2), both of which favor the contact of BDE209 with photogenerated holes and •OH species. The confirmation of efficient oxidative degradation and debromination of BDE209 is very important for finding new ways to remove polybrominated diphenyl ethers from the environment.
直接证据首次表明,在紫外光(λ>340nm)照射下,水相 TiO(2) 分散体中十溴二苯醚(BDE209)发生氧化降解。在紫外光照射下的乙腈分散体中,BDE209 在 TiO(2) 上几乎不会脱溴,但将水加入分散体中会大大增强其光催化氧化脱溴作用。在 12 小时的紫外光照射后,BDE209 在水相 TiO(2) 分散体中的脱溴效率高达 95.6%。BDE209 的光催化氧化导致生成芳香族开环中间体,如溴代二烯酸,进一步延长紫外光照射时间会导致这些中间体进一步降解。BDE209 的光催化氧化脱溴作用进一步通过以下观察结果得到证实:在不同含水量的水-乙腈混合物中,BDE209 的降解与•OH 自由基的形成呈正相关,而与光生电子无关。使用水不仅避免了有机溶剂对活性自由基的清除,而且增强了 BDE209 在 TiO(2)表面的吸附,这两者都有利于 BDE209 与光生空穴和•OH 物种的接触。确认 BDE209 的有效氧化降解和脱溴非常重要,因为这为从环境中去除多溴二苯醚找到了新途径。