Competition between electrochemical advanced oxidation and electrochemical hypochlorination of acetaminophen at boron-doped diamond and ruthenium dioxide based anodes

This work was undertaken to distinguish four pathways for the electrochemical oxidation of acetaminophen as a model organic substrate: (i) direct electron transfer from the substrate to the anode, (ii) reaction of the substrate with HO center dot at boron-doped diamond anodes, (iii) non-radical (two-electron) oxidation of the substrate at Ti/RuO2 anodes, and (iv) electrochemical hypochlorination if Cl- is present. Pathway (i) was isolated as a slow reaction when boron-doped diamond (BDD) was used as the anode in the range of water stability, whereas in the corresponding reaction with Ti/RuO2 only pathway (iii) could be detected. Pathway (ii) predominated for BDD in the potential range of water oxidation, and was the only mechanism leading to mineralization of the substrate. Comparison between chemical hypochlorination and electrochemical oxidation at Ti/RuO2 in the presence of chloride ion indicated that the latter process principally involves mediated hypochlorination. Oxidation at boron-doped diamond anodes in the presence of chloride was the most complex mechanistically, with competition between hypochlorination and the electrochemical "advanced oxidation process"; this led to the formation of chlorinated byproducts. The observation of mineralization under these conditions demonstrated cross-over between reaction pathways (ii) and (iv), even though hypochlorination appeared to be the initial pathway for loss of acetaminophen. The presence of chloride ion did not significantly retard mineralization of acetaminophen in the initial stages of oxidation, but significantly increased the energy requirement for complete mineralization. The results are discussed in the context of the use of electrochemical oxidation in waste management.