溴代阻燃剂六溴环十二烷（HBCD）在2013年被增列入《斯德哥尔摩公约》POPs黑名单，目前国内外仍缺乏有效的降解方法。受溴取代影响，HBCD具有接受电子还原降解的趋势。零价铝（ZVA，E0 = −1.66 V）是优良的电子供体，但在污染物去除领域的潜力尚未被充分开发。本项目通过ZVA的表面活化，先采用ZVA将HBCD还原脱溴，然后利用ZVA催化过硫酸盐产生强氧化性的硫酸根自由基（SO4•-）将还原中间产物氧化降解，建立一种两段式高效去除水中HBCD的新方法。研究内容包括：1）探讨HBCD存在时ZVA的表面腐蚀反应过程，获得适用于HBCD还原降解的ZVA活化方法和反应条件；2）考察HBCD的ZVA还原降解机理；3）阐明ZVA催化过硫酸盐的自由基机理及其对HBCD的氧化性能；4）揭示ZVA还原与SO4•-氧化的协同机制。本研究可为水中新兴污染物HBCD的去除提供理论和技术参考。

Hexabromocyclododecane (HBCD) is a widely used additive brominated flame retardant (BFR) and has therefore been widely detected in biota and other environmental matrices. Due to its bioaccumulation, long range transport, environmental persistence, and potential toxicity, HBCD was listed as one of the persistent organic pollutants (POPs) at the sixth meeting of the Stockholm Convention in 2013. Up till now, knowledge about the degradability of HBCD is very limited, and a fast and effective treatment technology for HBCD is urgently required. Comparing to its difficultly being oxidized, HBCD is theoretically easier to be reduced because of the substitution of Br atom. As an excellent electron donator, zero-valent aluminum (ZVA) [E0(Al3+/Al0) = −1.66 V] can provide a very strong thermodynamic driving force for the charge transfer, but the potential application of ZVA in the field of contaminant removal has not been explored until now. Therefore, in this proposal, we would develop a mild and effective removal technique for aqueous HBCD based on the simple combination of commercial Al powder with the common oxidants, persulfate or peroxymonosulfate. It is a sequential reduction/oxidation strategy (i.e. ZVA debromination followed by activated persulfate/peroxymonosulfate oxidation). Firstly, ZVA is used as a reductant to debrominate for HBCD. Then, the debrominated products could be rapidly oxidized by the generated sulfate radicals (SO4•-) [E0(SO4•-/SO42-) = +2.5 ~ +3.1 V] where ZVA is used as an activator. In this proposal, researches would focus on: 1) exploring the surface corrosion chemistry of ZVA with the presence of HBCD, so as to get the ZVA activation method and reaction parameters for HBCD degradation; 2) studying the reductive degradation mechanism of HBCD by ZVA; 3) obtaining the initial radical mechanism and the performance of ZVA-activated persulfate/peroxymonosulfate oxidation for HBCD degradation; and 4) revealing the synergistic effect of reduction and subsequent oxidation. Based on these researches, the reductive and oxidative reaction mechanism of HBCD degradation by the combined ZVA and persulfate/peroxymonosulfate system would be deeply understood, which could provide a theoretical and technological guide for the removal of the newly-emerging contaminant HBCD.