Understanding persulfate production at boron doped diamond film anodes

This research used molecular modeling and rotating disk electrode experiments (RDE) to investigate possible reaction pathways for persulfate production via electrolysis of sulfuric acid solutions using boron doped diamond (BDD) film anodes. Density functional theory (DFT) modeling indicated that uncatalyzed oxidation of SO₄^2- and HSO₄^-occurs at lower potentials than water oxidation, and that sulfate radical species (SO₄^-• and HSO₄^•) may be produced via direct electron transfer, or via reaction with hydroxyl radicals. The RDE experiments indicated that rates of persulfate generation were strongly dependent of the condition of the electrode surface, and that aged electrode surfaces favored water oxidation over direct SO₄² and HSO₄^- oxidation. Combination of sulfate radical species in solution is the lowest energy pathway for persulfate production. Sulfate radical species may also react with radical sites on the electrode surface and produce chemisorbed intermediates that can stabilize sulfate radical species. Reaction of the chemisorbed intermediates with a bisulfate radical can produce persulfate via a surface catalyzed pathway. However, the activation barriers for this pathway are much higher than those for persulfate production via solution phase species.