Photocatalytic ozonation in water treatment: Is there really a synergy between systems?

Numerous studies report on the synergy between ozonation and photocatalytic oxidation (TiO₂/UVA), which could open the way to the application of photocatalytic ozonation (PCOz) in water treatment. With the aim of establishing the existence of this synergy and its origin, in this work, using TiO₂ P25, 365 nm UVA LEDs and ozone transferred doses up to 5 mg (mg DOC₀)^-1 (DOC₀ 7 - 10 mg L^-1), a systematic study has been carried out featuring the effect of pH, alkalinity and water matrix in each of the systems involved in PCOz, with special attention to the role of organics adsorption onto TiO₂. In ultrapure water, an increase in pH and carbonates content exerted a slight negative effect on the photocatalytic degradation of primidone (low adsorption onto TiO₂ and mainly abated by free HO^•), this effect being higher on its mineralization. The negative effect of pH and alkalinity was much stronger for oxalic acid (high tendency to adsorb and mainly oxidized by positive holes). Accordingly, the results obtained at pH < pH_pzc (point of zero charge of the catalyst) in ultrapure water cannot at all be extrapolated to secondary effluents, since their composition negatively affects the photocatalytic performance. At the experimental conditions applied, only for the secondary effluent a synergy between O₃/UVA and TiO₂/UVA systems was observed. This synergy would be related, on the one hand, to the generation, from the matrix itself, of reactive entities or intermediates that promote the decomposition of ozone into HO^•; and, on the other hand, to an increase in catalyst activity as the matrix UVA absorption decreases, rather than from direct interactions between both systems. Despite de above, ozone requirement to achieve a significant reduction of DOC is high and would only be an interesting strategy for the elimination of ozone-refractory micropollutants.