Efficient mineralization of hydroperfluorocarboxylic acids with persulfate in hot water
Efficient mineralization of hydroperfluorocarboxylic acids with persulfate in hot water
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DOI：
10.1016/j.cattod.2010.02.023
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发表时间：
2010-04-15
期刊：
影响因子：
5.3
通讯作者：
Kutsuna, Shuzo
中科院分区：
文献类型：
--
作者：
Hori, Hisao;Murayama, Misako;Kutsuna, Shuzo
研究了过硫酸盐（S2 O 82-）诱导的H-PFCAs（HcnF 2nCOOH，n =4，6，8）在热水中的热分解，并与全氟羧酸（PFCAs）的热分解结果进行了比较.这是关于使用热水分解H-PFCAs的第一份报告，H-PFCAs正在开发作为环境持久性和生物累积性PFCAs的替代表面活性剂。虽然H-PFCAs在不存在S2 O 82-的情况下在80 ℃的热水中几乎没有分解，但向反应溶液中加入S2 O 82-导致有效矿化为F-离子，在处理6小时后F-产率[（F-摩尔数）/（初始H-PFCAs中氟的摩尔数）]为96.7-98.2%。S_2O_（82-）诱导的H-PFCAs在60 ℃下也能分解，其初始分解速率是相应PFCAs的7.1-12.7倍。反应机理可以通过SO 4中心点的亲核取代来解释-在连接到H-PFCAs的ω-H原子的碳原子上，然后形成全氟二羧酸（HOOCCn-1F 2n-2COOH），其与SO 4中心点反应得到较短链的全氟二羧酸：该过程最终导致完全矿化为F-离子。(C)2010 Elsevier B. V.保留所有权利。
The persulfate (S2O82-)-induced decomposition of hydroperfluorocarboxylic acids (H-PFCAs), that is, HCnF2n COOH (n =4, 6, and 8), in hot water was investigated, and the results were compared with the results for perfluorocarboxylic acids (PFCAs). This is the first report on the use of hot water to decompose H-PFCAs, which are being developed as alternative surfactants to environmentally persistent and bioaccumulative PFCAs. Although H-PFCAs showed almost no decomposition in hot water at 80 C in the absence of S2O82-, the addition of S2O82- to the reaction solution led to efficient mineralization to F- ions, with F- yields [(moles of F-)/(moles of fluorine in initial H-PFCAs)] of 96.7-98.2% after 6h of treatment. The decomposition of H-PFCAs induced by S2O82- also proceeded even at 60 C, at which the initial decomposition rates were 7.1-12.7 times those for the corresponding PFCAs. The reaction mechanism can be explained by nucleophilic substitution by SO4 center dot- at the carbon atom attached to the omega-H atom of the H-PFCAs, followed by formation of perfluorodicarboxylic acids (HOOCCn-1F2n-2COOH), which react with SO4 center dot- to give shorter-chain perfluorodicarboxylic acids: this process eventually resulted in complete mineralization to F- ions. (C) 2010 Elsevier B.V. All rights reserved.