Oxidative destruction of perfluorooctane sulfonate using boron-doped diamond film electrodes

Kimberly E. Carter, James Farrell

Research output: Contribution to journalArticlepeer-review

200 Scopus citations


This research investigated the oxidative destruction of perfluorooctane sulfonate at boron-doped diamond film electrodes. Experiments measuring oxidation rates of PFOS were performed over a range in current densitiesand temperatures using a rotating disk electrode (RDE) reactor and a parallel plate flow-through reactor. The oxidation of PFOS yielded sulfate, fluoride, carbon dioxide, and trace levels of trifluoroacetic acid. Reaction rates in the RDE reactor were zeroth order in PFOS concentration. Reaction rates in the flow-through reactor were mass-transfer-limited and were pseudo-first-order in PFOS concentration, with a half-life of 5.3 min at a current density of 20 mA/cm2. Eyring analysis of the zeroth order rate constants at a fixed electrode potential yielded an apparent activation energy of 4.2 kJ/mol for PFOS oxidation. Oensity functional theory (OFT) simulations were used to calculate activation barriers for different possible reaction mechanisms, including oxidation by hydroxyl radicals at different sites on the PFOS molecule, and direct electron transfer. A comparison of the experimentally measured apparent activation energy with those calculated using DFT indicated that the most likely rate-limiting step for PFOS oxidation was direct electron transfer.

Original languageEnglish (US)
Pages (from-to)6111-6115
Number of pages5
JournalEnvironmental Science and Technology
Issue number16
StatePublished - Aug 15 2008

ASJC Scopus subject areas

  • General Chemistry
  • Environmental Chemistry


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