6:2 多氟烷基磷酸二酯的电化学氧化——与羟基自由基的转化途径和反应动力学模拟,Environmental Science & Technology

当前位置： X-MOL 学术 › Environ. Sci. Technol. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

6:2 多氟烷基磷酸二酯的电化学氧化——与羟基自由基的转化途径和反应动力学模拟
Environmental Science & Technology ( IF 10.8 ) Pub Date : 2021-07-30 , DOI: 10.1021/acs.est.1c02106
Jonathan Zweigle ₁ , Boris Bugsel ₁ , Markus Schmitt ₁ , Christian Zwiener ₁

Affiliation

多氟烷基磷酸二酯 (diPAP) 广泛用于纸和纸板的浸渍，并通过生产过程和消费品的废物流排放。为了提高对 diPAPs 环境归宿的了解，电化学氧化 (EO) 用于表征转化途径和反应动力学。6:2 diPAP 被电化学转化为全氟羧酸（C ₅ -C ₇ PFCA）和两种中间体（6:2 含氟调聚物羧酸，FTCA 和 6:2 含氟调聚物不饱和羧酸，FTUCA）。潜在中间体 6:2 monoPAP 和 6:2 含氟调聚物醇 (FTOH) 的 EO 显示出相似的转化产物，但比例不同。我们表明 6:2 diPAP 是由 OH 自由基引发的 ( ^•OH）反应，就证明了的测得的稳态浓度^• OH与探针分子对苯二甲酸，淬火实验中，将反应的pH依赖性。PFHpA是6的主要产物：2 diPAP氧化，并且它被形成了针对其双分子速率常数被估计为伪一级反应

= 9.4（±1.4）×10 ⁷中号^-1小号^-1通过初始利率法。这可用于估计 6:2 diPAP 与^• OH反应的环境半衰期和持久性 PFCA 的形成动力学。

"点击查看英文标题和摘要"

Electrochemical Oxidation of 6:2 Polyfluoroalkyl Phosphate Diester—Simulation of Transformation Pathways and Reaction Kinetics with Hydroxyl Radicals

Polyfluoroalkyl phosphate diesters (diPAPs) are widely used for paper and cardboard impregnation and discharged via waste streams from production processes and consumer products. To improve the knowledge about the environmental fate of diPAPs, electrochemical oxidation (EO) was used to characterize the transformation pathways and reaction kinetics. 6:2 diPAP was transformed electrochemically to perfluorocarboxylic acids (C₅–C₇ PFCAs) and two intermediates (6:2 fluorotelomer carboxylic acid, FTCA, and 6:2 fluorotelomer unsaturated carboxylic acid, FTUCA). EO of potential intermediates 6:2 monoPAP and 6:2 fluorotelomer alcohol (FTOH) showed similar transformation products but with different ratios. We show that 6:2 diPAP is initiated by OH radical (^•OH) reactions, as evidenced by the measured steady-state concentrations of ^•OH with the probe molecule terephthalic acid, quenching experiments, and pH dependency of the reaction. PFHpA was the main product of 6:2 diPAP oxidation, and it was formed in a pseudo-first-order reaction for which a bimolecular rate constant was estimated to be

= 9.4(±1.4) × 10⁷ M^–1 s^–1 by an initial rate approach. This can be utilized to estimate the environmental half-life of 6:2 diPAP for the reaction with ^•OH and the formation kinetics of persistent PFCAs.

更新日期：2021-08-17

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南

全部期刊列表>>