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非离子表面活性剂极大地增强了纳米零价铁对多溴二苯醚的还原脱溴作用:机理与动力学。

Nonionic surfactant greatly enhances the reductive debromination of polybrominated diphenyl ethers by nanoscale zero-valent iron: mechanism and kinetics.

机构信息

School of Chemistry & Environment, Beihang University (BUAA), 37 Xueyuan Rd, Beijing 100191, China.

School of Chemistry & Environment, Beihang University (BUAA), 37 Xueyuan Rd, Beijing 100191, China.

出版信息

J Hazard Mater. 2014 Aug 15;278:592-6. doi: 10.1016/j.jhazmat.2014.06.030. Epub 2014 Jun 24.

Abstract

Nanoscale zero-valent iron (nZVI) has been considered as an effective agent for reductive debromination of polybrominated diphenyl ethers (PBDEs). But the high lipophilicity of PBDEs will hinder their debromination owing to the inefficient contact of PBDEs with nZVI. In this study, different ionic forms of surfactants were investigated aiming to promote PBDE debromination, and the beneficial effects of surfactant were found to be: nonionic polyethylene glycol octylphenol ether (Triton X-100, TX)>cationic cetylpyridinium chloride (CPC)>anionic sodium dodecyl benzenesulfonate (SDDBS). Except for with SDDBS, the promotion effect for PBDE debromination was positively related to the surfactant concentrations until a critical micelle concentration (CMC). The debromination process of octa-BDE and its intermediates could be described as a consecutive reaction. The corresponding rate constants (k) for the debromination of parent octa-BDE (including nona- to hepta-BDEs), the intermediates hexa-, penta-, and tetra-BDEs are 1.24 × 10(-1) h(-1), 8.97 × 10(-2) h(-1), 6.50 × 10(-2) h(-1) and 2.37 × 10(-3) h(-1), respectively.

摘要

纳米零价铁 (nZVI) 已被认为是还原脱溴多溴二苯醚 (PBDEs) 的有效试剂。但由于 PBDEs 的高疏水性,它们与 nZVI 的接触效率会很低,从而阻碍其脱溴。在这项研究中,考察了不同离子形式的表面活性剂,旨在促进 PBDE 的脱溴,发现表面活性剂具有以下有益效果:非离子型聚乙二醇辛基苯基醚(Triton X-100,TX)>阳离子十六烷基氯化吡啶(CPC)>阴离子十二烷基苯磺酸钠(SDDBS)。除 SDDBS 外,PBDE 脱溴的促进效果与表面活性剂浓度呈正相关,直至达到临界胶束浓度(CMC)。八溴联苯醚及其中间产物的脱溴过程可以描述为连续反应。母体八溴联苯醚(包括九溴至七溴联苯醚)、中间体六溴、五溴和四溴联苯醚的脱溴相应速率常数 (k) 分别为 1.24×10(-1) h(-1)、8.97×10(-2) h(-1)、6.50×10(-2) h(-1) 和 2.37×10(-3) h(-1)。

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