Experimental insights into anodic oxidation of hexafluoropropylene oxide dimer acid (GenX) on boron-doped diamond anodes

GenX is the trade name of the ammonium salt of hexafluoropropylene oxide dimer acid (HFPO-DA) and is used as a replacement for the banned perfluorooctanoic acid (PFOA). However, recent studies have found GenX to be more toxic than PFOA. This work deals with the electrochemical degradation of HFPO-DA using boron-doped diamond anodes. For the first time, an experimental study was conducted to investigate the influence of sulfate concentration and other operating parameters on HFPO-DA degradation. Results demonstrated that sulfate radicals were ineffective in HFPO-DA degradation due to steric hindrance by –CF₃ branch. Direct electron transfer was found as the rate-determining step. By comparing degradation of HFPO-DA with that of PFOA, it was observed that the steric hindrance by –CF₃ branch in HFPO-DA decreased the rate of electron transfer from the carboxyl head group even though its defluorination rate was faster. Conclusively, a degradation pathway is proposed in which HFPO-DA mineralizes to CO₂ and Fˉ via formation of three intermediates.