Non-toxic fluorine-doped TiO2 nanocrystals from TiOF2 for facet-dependent naproxen degradation

In the present study, the photocatalytic degradation of naproxen (NPX), which is a nonsteroidal anti-inflammatory drug (NSAID), frequently detected in drinking water, was investigated. The F-doped TiO2 with defined morphology was successfully obtained from TiOF2 and applied for photocatalytic degradation under UV–vis and visible light. All samples were characterised by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, zeta potential, diffuse reflectance spectroscopy, and Brunauer–Emmett–Teller surface area analyses. The effect of morphology on the photocatalytic activity of the F-TiO2 nanostructures with exposed {1 0 1}, {0 0 1} and {1 0 0} facets was studied. Octahedral F-TiO2 particles with exposed {1 0 1} facets revealed the highest photocatalytic activity, and degraded 100% of the initial NPX concentration after 40 min of the photodegradation process under simulated solar light (UV–vis). Moreover, this sample exhibited the highest TOC removal and NPX degradation under visible light (>420 nm). Based on HPLC-MS analysis, it was assumed that {0 0 1} facets present in fluorinated decahedral nanostructures promote the formation of a dimer, which further hinders the mineralisation rate. Therefore, decahedral nanostructures exposing {1 0 1} and {0 0 1} facets revealed lower photocatalytic activity than octahedral F-TiO2 particles with exposed {1 0 1} facets, which is also consistent with DFT studies. Finally, toxicity assessment of post-process suspensions using Microtox bioassay confirmed that fluorine-doped octahedral anatase particles are non-toxic, although fluorine ions were the reactants of the synthesis from TiOF2. Overall results showed the possibility of application of highly efficient and environmentally safe fluorine-doped anatase photocatalysts in improved degradation of naproxen.