Defluorination and Mineralization of Difluorophenols in Water by Anodic Contact Glow Discharge Electrolysis

Abstract

Anodic contact glow discharge electrolysis (CGDE) is a DC-excited atmospheric pressure discharge, in which a steady non-thermal plasma is generated locally between the surface of an electrolytic solution and an anode in contact with it. The I–U characteristics of CGDE were investigated. The plasma temperatures were estimated to be in the range, 1373–2045 K. Hydroxyl radicals and hydrogen peroxide were the main oxidants generated by CGDE. The hydrogen peroxide concentration reached 31.2 mmol/L (mM) in a phosphate buffer solution without organic substrates. During CGDE, the DFPs and the corresponding total organic carbon (TOC) in water were consumed. Most of the fluorine atoms in the DFPs were converted to fluoride ions, and the fluoride concentration increased steadily. An analysis of the hydroxylation of DFPs suggested that the hydroxyl radicals generated by CGDE were the key species responsible for the degradation of DFPs, and the possible mechanistic routes of the mineralization of DFPs are proposed. The disappearance of DFPs and the TOC as well as the defluorination of the DFPs followed first-order kinetics. The rate of TOC disappearance was relatively constant: 1.00 ± 0.05 × 10−2 min−1. The order of disappearance of the DFPs was 2,6-DFP > 2,3-DFP > 2,5-DFP > 2,4-DFP > 3,4-DFP > 3,5-DFP. In contrast, the order of defluorination of the DFPs was 2,5-DFP > 2,3-DFP > 2,6-DFP > 2,4-DFP > 3,4-DFP > 3,5-DFP. Overall, the order of the reaction rates for each DFP was kDFP > kdF > kTOC.