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Ti/SnO2-Sb-Ce、Ti/SnO2-Sb/Ce-PbO2 和 Ti/BDD 电极高效温和电化学矿化长链全氟羧酸(C9-C10)。

Highly efficient and mild electrochemical mineralization of long-chain perfluorocarboxylic acids (C9-C10) by Ti/SnO2-Sb-Ce, Ti/SnO2-Sb/Ce-PbO2, and Ti/BDD electrodes.

机构信息

State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University , Beijing 100875, P.R. China.

出版信息

Environ Sci Technol. 2013 Nov 19;47(22):13039-46. doi: 10.1021/es4034414. Epub 2013 Oct 28.

Abstract

The electrochemical mineralization of environmentally persistent long-chain perfluorinated carboxylic acids (PFCAs), i.e., perfluorononanoic acid (C8F17COOH, PFNA) and perfluorodecanoic acid (C9F19COOH, PFDA) was investigated in aqueous solutions (0.25 mmol L(-1)) over Ti/SnO2-Sb-Ce (SnO2), Ti/SnO2-Sb/Ce-PbO2 (PbO2), and Ti/BDD (BDD) anodes under galvanostatic control at room temperature. Based on PFCA decay rate, total organic carbon (TOC) reduction, defluorination ratio, safety, and energy consumption, the performance of PbO2 electrode was comparable with that of BDD electrode. After 180 min electrolysis, the PFNA removals on BDD and PbO2 electrodes were 98.7 ± 0.4% and 97.1 ± 1.0%, respectively, while the corresponding PFDA removals were 96.0 ± 1.4% and 92.2 ± 1.9%. SnO2 electrode yielded lower PFCA removals and led to notable secondary pollution by Sb ions. The primary mineralization product, F(-), as well as trace amounts of intermediate PFCAs with shortened chain lengths, were detected in aqueous solution after electrolysis. On the basis of these results, a degradation mechanism including three potential routes is proposed: via formation of short-chain PFCAs by stepwise removal of CF2; direct mineralization to CO2 and HF; conversion to volatile fluorinated organic compounds. The results presented here demonstrate that electrochemical technique exhibits high efficiency in mineralizing PFNA and PFDA under mild conditions, and is promising for the treatment of long-chain PFCAs in wastewater.

摘要

在室温下,通过恒电流控制,在水溶液(0.25mmol/L)中研究了环境持久性长链全氟羧酸(PFCAs),即全氟壬酸(C8F17COOH,PFNA)和全氟癸酸(C9F19COOH,PFDA)在 Ti/SnO2-Sb-Ce(SnO2)、Ti/SnO2-Sb/Ce-PbO2(PbO2)和 Ti/BDD(BDD)阳极上的电化学矿化。基于 PFCAs 衰减率、总有机碳(TOC)去除率、脱氟率、安全性和能耗,PbO2 电极的性能可与 BDD 电极相媲美。在 180min 的电解后,BDD 和 PbO2 电极上的 PFNA 去除率分别为 98.7±0.4%和 97.1±1.0%,而相应的 PFDA 去除率分别为 96.0±1.4%和 92.2±1.9%。SnO2 电极的 PFCAs 去除率较低,并导致 Sb 离子的显著二次污染。在电解后,水溶液中检测到主要的矿化产物 F-以及痕量的短链 PFCAs 中间产物。基于这些结果,提出了一种包括三条潜在途径的降解机制:通过逐步去除 CF2形成短链 PFCAs;直接矿化为 CO2和 HF;转化为挥发性含氟有机化合物。本研究结果表明,电化学技术在温和条件下对 PFNA 和 PFDA 的矿化具有高效性,有望用于处理废水中的长链 PFCAs。

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