Influence of Fluorine Doping on Rutile TiO Nanostructures for Visible-Light-Driven Photocatalysis: A DFT + U Study.

In this work, a density functional theory (DFT) with Hubbard correction (U) approaches implemented through the Quantum ESPRESSO code is utilized to investigate the effects of fluorine (F) doping on the structural, electronic, and optical properties of rutile TiO. Rutile TiO is a promising material for renewable energy production and environmental remediation, but its wide bandgap limits its application to the UV spectrum, which is narrow and expensive. To extend the absorption edge of TiO into the visible light range, different concentrations of F were substituted at oxygen atom sites. The structural analysis reveals that the lattice constants and bond lengths of TiO increased with F concentrations. Ab initio molecular dynamics simulations (AIMD) at 1000 K confirm that both pristine and F-doped rutile TiO maintains structural integrity, indicating excellent thermal stability essential for high-temperature photocatalytic applications. Band structure calculations show that pure rutile TiO has a bandgap of 3.0 eV, which increases as the F concentration rises, with the 0.25 F-doped structures exhibiting an even larger bandgap, preventing it from responding to visible light. The absorption edge of doped TiO shifts towards the visible region, as shown by the imaginary part of the dielectric function. This research provides valuable insights for experimentalists, helping them understand how varying F concentrations influence the properties of rutile TiO for photocatalytic applications.