Consequences of Nitrogen Doping and Oxygen Enrichment on Titanium Local Order and Photocatalytic Performance of TiO₂ Anatase

Extended X-ray absorption fine structure (EXAFS) investigation of the oxygen-rich titania formed via the thermal treatment of N-doped TiO₂ has revealed that the removal of N-dopants is responsible for the creation of defect sites in the titanium environment, thus triggering at high temperatures (500–800 °C) the capture of atmospheric oxygen followed by its diffusion toward the vacant sites and formation of interstitial oxygen species. The effect of the dopants on Ti coordination number and Ti–O_int and Ti–N_int bond distances has been estimated. The photocatalytic <i>p</i>-cresol degradation tests have demonstrated that the interband states formed by the N-dopants contribute to a greater extent to the visible-light activity than the oxygen interstitials do. However, under the UV irradiation the oxygen-rich titania shows higher efficiency in the pollutant degradation, while the N-dopants in N–TiO₂ play the role of recombination sites. The presence of the surface nitrogen species in TiO₂ is highly beneficial for the application in partial photooxidation reactions, where N–TiO₂ demonstrates a superior selectivity of 5-hydroxymethyl furfural (HMF) oxidation to 2,5-furandicarbox­aldehyde (FDC). Thus, this work underlines the importance of a rational design of nonmetal doped titania for photocatalytic degradation and partial oxidation applications, and it establishes the role of bulk defects and surface dopants on the TiO₂ photooxidation performance