Department of Environmental Sciences and Energy Research, Weizmann Institute of Science, Rehovot, Israel.
Chemosphere. 2013 Sep;93(1):172-7. doi: 10.1016/j.chemosphere.2013.05.026. Epub 2013 Jun 17.
The catalytic degradation of two brominated flame retardants (BFRs), tribromoneopentyl alcohol (TBNPA) and 2,4 dibromophenol (2,4-DBP) by copper oxide nanoparticles (nCuO) was investigated. The degradation kinetics, the debromination, and the formation of intermediates by nCuO catalysis were also compared to Fenton oxidation and nano zero-valent iron (nZVI) reduction methods. BFRs have been added to various products like plastic, textile, electronics and synthetic polymers at growing rates. In spite of the clear advantages of reducing fire damages, many of these BFRs may be released to the environment after their beneficial use and become contaminants. The two studied BFRs were fully degraded with sufficient time (hours to days) and oxidation agent (H2O2). Shorter reaction times showed differences in reaction pathway and kinetics. The 2,4-DBP showed faster degradation than TBNPA, by nCuO catalysis. Relatively high resistance to degradation was recorded for 2,4-DBP with nZVI, yielding 20% degradation after 24h, while the TBNPA was degraded by 85% within 12h. Electron Spin Resonance (ESR) measurements show generation of both hydroxyl and superoxide radicals. In addition, inhibition of 2,4-DBP degradation in the presence of spin traps implies a radical degradation mechanism. A catalytic mechanism for radical generation and BFR degradation by nCuO is proposed. It is further suggested that H2O2 plays an essential role in the activation of the catalyst.
纳米氧化铜(nCuO)催化降解两种溴化阻燃剂(BFRs),三溴新戊醇(TBNPA)和 2,4-二溴苯酚(2,4-DBP)。还比较了 nCuO 催化作用下的降解动力学、脱溴和中间产物的形成,与芬顿氧化和纳米零价铁(nZVI)还原方法相比。BFRs 已以越来越快的速度添加到塑料、纺织品、电子产品和合成聚合物等各种产品中。尽管减少火灾损失有明显的优势,但这些 BFRs 中的许多在其有益使用后可能会释放到环境中,并成为污染物。两种研究的 BFRs 在足够的时间(数小时至数天)和氧化剂(H2O2)下完全降解。较短的反应时间显示出不同的反应途径和动力学。2,4-DBP 通过 nCuO 催化作用比 TBNPA 降解得更快。nZVI 对 2,4-DBP 的降解具有相对较高的抵抗力,24 小时后仅降解 20%,而 TBNPA 在 12 小时内降解 85%。电子顺磁共振(ESR)测量表明同时生成了羟基和超氧自由基。此外,在存在自旋陷阱的情况下抑制 2,4-DBP 降解表明存在自由基降解机制。提出了一种由 nCuO 产生自由基和 BFR 降解的催化机制。进一步表明 H2O2 在催化剂的活化中起着重要作用。