Debromination of polybrominated diphenyl ethers by nanoscale zerovalent iron: pathways, kinetics, and reactivity.
Debromination of polybrominated diphenyl ethers by nanoscale zerovalent iron: pathways, kinetics, and reactivity.
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DOI：
10.1021/es101601s
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发表时间：
2010-11-01
影响因子：
11.4
通讯作者：
Luthy, Richard G.
中科院分区：
文献类型：
--
作者：
Zhuang, Yuan;Ahn, Sungwoo;Luthy, Richard G.
研究了纳米级零价铁颗粒 (nZVI) 对选定的多溴二苯醚 (PBDE) 的脱溴，以研究 PBDE 的降解途径和反应动力学。研究的主要 PBDE 是 2,3,4-三溴二苯醚 (BDE 21)，以评估降解途径。 nZVI 可以有效地将选定的 PBDE 脱溴成低溴化合物和二苯醚（PBDE 的完全脱溴形式）。通过对单侧溴（2,3-二BDE 和 3,4-二BDE）和无侧侧（三种单BDE）溴的 PBDE 脱溴试验观察了 nZVI 对偏溴的敏感性。尽管对于在同一苯环上具有两个相邻溴的二溴二苯醚来说，同时多步脱溴似乎是合理的，但观察到从正溴二苯醚到(n-1)-溴二苯醚的逐步脱溴是主要的反应过程。反应速率常数是通过假设 PBDE 和 nZVI 之间的反应是伪一级反应来估计的，并且速率随着溴取代基的减少而降低。反应速率常数与相应化合物的形成热和最低未占据分子轨道的能量相关，这些似乎是 PBDE 同系物组之间相对反应速率的有用描述符。
The debromination of selected polybrominated diphenyl ethers (PBDEs) by nanoscale zerovalent iron particles (nZVI) was studied to investigate the degradation pathways and the reaction kinetics of the PBDEs. The primary PBDE investigated was 2,3,4-tribromo diphenyl ether (BDE 21) to assess degradation pathways. nZVI could effectively debrominate the selected PBDEs into lower brominated compounds and diphenyl ether, a completely debrominated form of PBDEs. The susceptibility of the meta-bromine by nZVI was observed from the debromination tests for PBDEs with single-flanked (2,3-diBDE and 3,4-diBDE) and unflanked (three monoBDEs) bromines. The stepwise debromination from n-bromo- to (n-1)-bromodiphenyl ether was observed as the dominant reaction process, although simultaneous multistep debromination seemed to be plausible for di-BDEs having two bromines adjacent on the same phenyl ring. The reaction rate constants were estimated by assuming the reaction between PBDEs and nZVI was a pseudo-first order reaction and the rates decreased with fewer bromine substituents. The reaction rate constants were correlated with the heat of formation and the energy of the lowest unoccupied molecular orbital of the corresponding compounds, and these appear to be useful descriptors of relative reaction rates among PBDE homologue groups.
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影响因子：
4.1
作者：
Ciparis, S;Hale, RC
通讯作者：
Hale, RC
影响因子：
11.4
作者：
Li, An;Tai, Chao;Hu, Jingtian
通讯作者：
Hu, Jingtian
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影响因子：
11.4
作者：
Fu, QS;Barkovskii, AL;Adriaens, P
通讯作者：
Adriaens, P
影响因子：
11.4
作者：
Joo, SH;Feitz, AJ;Waite, TD
通讯作者：
Waite, TD
影响因子：
11.8
作者：
Hale, RC;Alaee, M;Ikonomou, MG
通讯作者：
Ikonomou, MG