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Electrochemical oxidation of 1H,1H,2H,2H-perfluorooctane sulfonic acid (6:2 FTS) on DSA electrode:Operating parameters and mechanism
作者姓名:Qiongfang Zhuo  Xiang Li  Feng Yan  Bo Yang  Shubo Deng  Jun Huang  Gang Yu
作者单位:POPs Research Center, School of Environment, Tsinghua University, Beijing 100084, China;South China Institute of Environmental Sciences, the Ministry of Environment Protection, Guangzhou 510655, China;POPs Research Center, School of Environment, Tsinghua University, Beijing 100084, China;POPs Research Center, School of Environment, Tsinghua University, Beijing 100084, China;College of Chemistry and Chemical Engineering, Shenzhen University, Shenzhen 518060, China;POPs Research Center, School of Environment, Tsinghua University, Beijing 100084, China;POPs Research Center, School of Environment, Tsinghua University, Beijing 100084, China;POPs Research Center, School of Environment, Tsinghua University, Beijing 100084, China
基金项目:supported by the National Natural Science Foundation of China (No.21307036); the National High-Tech Research and Development Program of China (No.2013AA062705); the National Key Scientific and Technological Project for Water Pollution Control and Management (Nos.2012ZX07206-002,2012ZX07206-003)
摘    要:The 6:2 FTS was the substitute for perfluorooctane sulfonate(PFOS) in the chrome plating industry in Japan. Electrochemical oxidation of 6:2 FTS was investigated in this study. The degradabilities of PFOS and 6:2 FTS were tested on the Ti/SnO2–Sb2O5–Bi2O3anode. The effects of current density,potential,and supporting electrolyte on the degradation of 6:2 FTS were evaluated. Experimental results showed that 6:2 FTS was more easily degraded than PFOS on the Ti/SnO2–Sb2O5–Bi2O3anode. At a low current density of 1.42 mA/cm2,6:2 FTS was not degraded on Ti/SnO2–Sb2O5–Bi2O3,while the degradation ratio increased when the current density ranged from 4.25 to 6.80 mA/cm2. The degradation of 6:2 FTS at current density of 6.80 mA/cm2 followed pseudo first-order kinetics with the rate constant of 0.074 hr-1. The anodic potential played an important role in the degradation of 6:2 FTS,and the pseudo first-order rate constants increased with the potential. The surface of Ti/SnO2–Sb2O5–Bi2O3was contaminated after electrolysis at constant potential of 3 V,while the fouling phenomenon was not observed at 5 V. The fouled anode could be regenerated by incinerating at 600°C. The intermediates detected by ultra-performance liquid chromatography coupled with a triple-stage quadrupole mass spectrometer(UPLC–MS/MS) were shorter chain perfluorocarboxylic acids. The 6:2 FTS was first attacked by hydroxyl radical,and then formed perfluorinated carboxylates,which decarboxylated and removed CF2 units to yield shorter-chain perfluorocarboxylic acids.

关 键 词:电化学氧化  全氟辛烷  FTS  DSA电极  磺酸  工作参数  SnO2薄膜  超高效液相色谱
收稿时间:21 August 2013
修稿时间:29 January 2014
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