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In recent times, some researchers have successfully demonstrated the efficacy of UV photolysis of electrochemically generate free chlorine (UV/electro-chlorine) as for an advanced oxidation process. Since bromine as well as chlorine is an element belonging to halogen, it is expected that UV photolysis of electrochemically generated free bromine (UV/electro-bromine) also shows an advanced oxidation effect. To elucidate the feasibility of UV/electro-bromine system, its advanced oxidation mechanism was investigated using radical probes of 1,4-dioxane and nitrobenzene. In contrast to the UV/electro-chlorine system, the advanced oxidation effect of UV/electro-bromine system was inhibited under acidic conditions due to the accumulation of photochemically inert Br 2 . The most abundant radical in UV/electro-bromine system was dibromine radical anion (Br 2 ˙ − ) and the second-order reaction rate constant of Br 2 ˙ −  with 1,4-dioxane was estimated to be 2.4 × 10 5  M −1  s −1 . As a result of the abundance and the reactivity of Br 2 ˙ − , it was the main contributor to 1,4-dioxane degradation. On the other hand, nitrobenzene was mainly decomposed by direct UV photolysis because Br 2 ˙ −  does not react with nitrobenzene. The contribution of hydroxyl radical (HO˙) to 1,4-dioxane degradation was much lower than that of Br 2 ˙ −  because its concentration was 4–5 order of magnitude lower than that of Br 2 ˙ − . However, the HO˙ concentration elevated with a decrease in the concentration of bromide ion (Br − ). Consequently, the reactivity of Br 2 ˙ −  with pollutants and the Br −  concentration have critical impacts on the advanced oxidation performance of UV/electro-bromine system.

Advanced oxidation mechanism of UV photolysis of electrochemically generated free bromine