Electrochemical oxidation of 1H,1H,2H,2H-perfluorooctane sulfonic acid (6：2 FTS) on DSA electrode：Operating parameters and mechanism
Qiongfang Zhuo , Xiang Li , Feng Yan , Bo Yang , Shubo Deng , Jun Huang , Gang Yu
DOI:10.1016/j.jes.2014.05.042
Received August 21, 2013,Revised April 11, 2014, Accepted , Available online August 28, 2014
Volume 26,2014,Pages 1733-1740
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 FTSwere tested on the Ti/SnO2-Sb2O5-Bi2O3 anode. The effects of current density, potential, and supporting electrolyte on the degradation of 6:2 FTS were evaluated. Experimental results showed that 6:2 FTSwas more easily degraded than PFOS on the Ti/SnO2-Sb2O5-Bi2O3 anode. 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-Bi2O3 was 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℃. 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.
