A proof of the direct hole transfer in photocatalysis: The case of melamine

Abstract

The photoinduced transformation of 2,4,6-triamino-1,3,5-triazine (melamine) was studied by using different advanced oxidation technologies under a variety of experimental conditions. The systems involving homogeneous hydroxyl radicals, as generated by H2O2/hν, Fenton reagent, and sonocatalysis are ineffective. However, melamine is degraded under photocatalytic conditions or by SO4− (S2O82−/hν). The time evolution of long-living intermediates, such as 2,4-diamino-6-hydroxy-1,3,5-triazine (ammeline) and 2-amino-4,6-dihydroxy-1,3,5-triazine (ammelide), has been followed, being 2,4,6-trihydroxy-1,3,5-triazine (cyanuric acid) the final stable product. During both photocatalytic and S2O82−/hν experiments, in the early steps, a fairly stable intermediate evolving to ammelide is observed in a large extent. This intermediate was identified as 2,4-diamino-6-nitro-1,3,5-triazine. This indicates that the primary photocatalytic event is the oxidation of the amino-group to nitro-group through several consecutive fast oxidation steps, and that a hydrolytic step leads to the release of nitrite in solution. To elucidate the nature of the oxidant species hole scavengers such as methanol and bromide ions were added to the irradiated TiO2. They completely stop the degradation, whereas chloride and fluoride ions decrease the degradation rate.The study of the photocatalytic degradation rate of melamine at increasing concentrations using two different commercial titanium dioxides, such as P25 and Merck TiO2, showed an intriguing behavior. A drastic abatement of the melamine transformation rate was observed when coagulation of the P25 slurry occurs due both to the pH change and melamine concentration effect that increase melamine adsorption. In the presence of TiO2 (Merck) the melamine initial degradation rates are significantly lower than those observed in the presence of P25 but are not depressed at larger concentrations. The experimental evidences (e.g., absence of melamine adsorption onto TiO2 surface at low concentrations or at acidic pH or due to the catalyst surface texture, and the lack of reactivity toward OH free and bound) suggest that the effective photocatalytic mechanism is based on an outer sphere direct hole transfer to the melamine. Its formal potential lies in the range 1.9–2.3V vs NHE. Then, the photodegradation of melamine is an efficient tool to evaluate the direct hole transfer ability of a photocatalyst.