Photocatalytic degradation of ibuprofen using titanium oxide: insights into the mechanism and preferential attack of radicals.

Abstract

The present work studied ibuprofen degradation using titanium dioxide as a photocatalyst. Mechanistic aspects were presented and the preferred attack sites by the OH˙ radical on the ibuprofen molecule were detailed, based on experimental and simple theoretical-computational results. Although some previous studies show mechanistic proposals, some aspects still need to be investigated, such as the participation of 4-isobutylacetophenone in the ibuprofen degradation and the preferred regions of attack by OH˙ radicals. The photodegradation was satisfactory using 0.03 g of TiO2 and pH = 5.0, reaching 100% decontamination in 5 min. The zeta potential curve showed the regions of attraction and repulsion between TiO2 and ibuprofen, depending on the pH range and charge of the species, influencing the amount of by-products formed. Different by-products have been identified by GC-MS, such as 4-isobutylacetophenone. Ibuprofen conversion to 4-isobutylacetophenone takes place through decarboxylation reaction followed by oxidation. The proposed mechanism indicates that the degradation of ibuprofen undergoes a series of elementary reactions in solution and on the surface. Three different radicals (OH˙, O2−˙ and OOH˙) are produced in the reaction sequence and contribute strongly to the oxidation and mineralization of ibuprofen and by-products, but the hydroxyl radical has a greater oxidation capacity. The simple study using the DFT approach demonstrated that the OH˙ radical attacks preferentially in the region of the ibuprofen molecule with high electronic density, which is located close to the aromatic ring (C Created by potrace 1.16, written by Peter Selinger 2001-2019 ]]> C bond). The presence of the OH˙ radical was confirmed through a model reaction using salicylic acid as a probe molecule.