Temperature and nitrogen-induced modification of activated carbons for efficient catalytic ozonation of salicylic acid as a model emerging pollutant.

The occurrence of emerging pollutants on effluents of wastewater treatment plants makes unfeasible their reutilization and consequently to comply with the sixth goal of 2030 Agenda for sustainable development. Thus, it is extremely important to find ways to remove these pollutants without compromising the quality of reclaimed water. Ozonation has been successfully explored for this purpose, but it still presents limitations towards some oxidant-resistant pollutants. To surpass this, the conversion of ozone (O3) into more reactive species is required, which can be accomplished by using catalysts. Carbon catalysts, such as activated carbons (ACs), represent a more environmentally attractive option than traditional metal-based catalysts, with the advantage of being easily modified to tune their textural and surface properties to the reaction chemistry. In this study, two different sources of ACs were tested in the catalytic ozonation of a frequently detected emerging pollutant: salicylic acid (SalAc). These ACs were submitted to thermal treatment under H2 and functionalization with N precursors, such as melamine and poly(ethyleneimine), to induce changes in the surface properties, especially in the nitrogen content. Although no correlation was found between the N-content and catalytic activity, the thermal treatment under H2 increased the mesopores surface area (Smeso), which reflected in greater catalytic activity. As that, the best-performing AC was the one with the highest Smeso, which revealed also to be resistant to O3 and able to convert O3 into more reactive species, evidenced by the capacity of oxalic acid, a well-known ozone-resistant by-product. The same AC was then submitted to three consecutive reutilization cycles and a more significant activity loss was observed in terms of SalAc degradation rate (⁓ 40%) then total organic carbon removal (⁓ 25%), from the first to the third cycle. This decline in efficiency was ascribed to the presence of by-products adhered to the catalyst surface, which impede its ability to react effectively with O3.

Photocatalytic ozonation of aniline with TiO2-carbon composite materials.

The photocatalytic ozonation of aniline (ANL) aqueous solutions was carried out in the presence of neat titanium dioxide (TiO2), multi-walled carbon nanotubes (MWCNT) and a composite of TiO2 and MWCNT. Independent tests for catalytic ozonation and photocatalysis were also carried out in order to explore the potential occurrence of a synergetic effect. Photocatalytic and catalytic ozonation carried out with an ozone dose of 50 g m-3 converted ANL in 15 min. Photocatalysis using P25, commercial TiO2, and an 80:20 (w/w) composite of P25 and MWCNT also led to total ANL conversion, but at longer reaction times. Removal of TOC was higher than 70% for all photocatalytic ozonation systems at 1 h of reaction. With the exception of neat MWCNT, photocatalytic ozonation in the presence of the selected samples led to nearly complete mineralization after 3 h of reaction. Photocatalytic ozonation completely removed oxalic acid (OXA) formed during ANL degradation. The concentration of oxamic acid (OMA, other ANL degradation by-product more refractory than OXA) generally increased with time, and in the photocatalytic ozonation with P25 based materials its concentration decreased earlier. The presence of nitrates and ammonium was confirmed during ANL degradation by all tested treatments, with the exception of the cation in TiO2 catalysed reactions.

Removal of oxalic acid, oxamic acid and aniline by a combined photolysis and ozonation process.

Aniline (ANL), an aromatic amine, oxalic acid (OXA) and oxamic acid (OMA), short-chain carboxylic acids, were chosen as model organic pollutants for testing the combined effect of neat photolysis and ozonation in the treatment of aqueous effluents. In order to better understand the results, single ozonation and neat photolysis were also carried out. OXA has a high refractory character relatively to single ozonation and neat photolysis only accounted for 26% conversion of OXA after 2 h of reaction. On the other hand, OXA complete degradation was observed in less than an hour when ozone and light were used simultaneously. Despite OMA, a compound never studied before by a combined ozonation and photolysis treatment, being highly refractory to oxidation, more than 50% was removed by photo-ozonation after 3 h of reaction. In the case of ANL, both single ozonation and photo-ozonation resulted in 100% removal in a short reaction period due to the high reactivity of ozone to attack this type of molecules; however, only the combined method leads to efficient mineralization (89%) after 3 h of reaction. A significant synergetic effect was observed in the degradation of the selected contaminants by the simultaneous use of ozone and light, since the mineralization rate of combined method is higher than the sum of the mineralization rates of the individual treatments. The promising results observed in the degradation of the selected contaminants are paving the way to the application of photo-ozonation in the treatment of wastewater containing this type of pollutants.

Composites of manganese oxide with carbon materials as catalysts for the ozonation of oxalic acid.

Manganese oxide and manganese oxide-carbon composites were prepared and tested as catalysts for the removal of oxalic acid by ozonation. Their performances were compared with the parent carbon material (activated carbon or carbon xerogel) used to prepare the composites. Oxalic acid degradation by carbon materials is slower than that attained with manganese oxide or manganese oxide-carbon composites. A complete degradation after 90 and 45 min of reaction was obtained for carbon materials and for the catalysts containing manganese, respectively. The ozonation in the presence of the prepared composites are supposed to occur mainly by surface reactions, following a direct oxidation mechanism by molecular ozone and/or surface oxygenated radicals.