Photocatalytic selective oxidation of ammonia in a semi-batch reactor: Unravelling the effect of reaction conditions and metal co-catalysts

Photocatalysis has been used for the oxidation of ammonia/ammonium in water. A semibatch photoreactor was developed for this purpose, and nanostructured TiO2-based materials, either commercial P25 or prepared by flame spray pyrolysis (FSP), were used as catalysts. In the present work, we investigated the effect of (i) metal co-catalysts, (ii) pH, and (iii) ammonia concentration on the efficiency of oxidation and on the selectivity to the undesired overoxidation byproduct, i.e., nitrites and nitrates. Several metals were added to both titania samples, and the physicochemical properties of every sample were studied by XRD, BET, and UV-Vis spectroscopy. The pH, which was investigated in the range of 2.5–11.5, was the most important parameter. The optimum pH values, resulted as 11.5 and 4.8 for P25 and FSP respectively, matching the best compromise between an acceptable conversion and a limited selectivity toward nitrite and nitrate formation. For both titania samples (P25 and FSP), ammonia conversion vs. nitrite and nitrate formation were highly dependent on the pH. At pH ≥ 9, the initial rate of photooxidation was high, with selective formation of overoxidized byproducts, whereas, at a more acidic pH, the conversion was lower, but the selectivity toward nitrogen formation was higher. P25 samples added with noble metal co-catalysts (0.1 mol% Ag, Au, Pd, Pt) at pH = 11.5 remarkably increased the selectivity to nitrite and nitrate, while, in the case of FSP samples (pH = 4.8), the co-catalysts increased the selectivity toward N2 with respect to the unpromoted catalyst and also the conversion in the case of Au and Pt. Reactivity was discussed, leading to the proposing of a mechanism that correlates the activity with either surface adsorption (depending of the surface charge of the catalyst and on pH) or the homogeneous reactivity of oxidizing species.