Tailoring the electronic properties of TiO$_2$ monolayers for solar driven catalysis through transition metal doping (2410.08358v1)

Abstract: Substitutional doping with transition metals is carried out in the Lepidocrocite phase - the stable monolayer geometry of TiO$_2$, using density functional theory (DFT) methods. The doping is carried out at the differently coordinated O atom cites, producing Janus monolayer geometries. Our results indicate that key fundamental properties for photocatalysis can be tuned via doping. Monolayers doped with Ag, Au, Pd and Pt are thermodynamically stable, amongst all considered doping possibilities, as evident from phonon band structure calculations. Electronic structure of the Janus monolayers alters significantly, compared to pristine TiO$_2$, owing to the emergence of mid-gap states. Reduced band gap arises from upward shift of the valence band, suggesting enhanced visible-light response. Dopant atoms also introduce excess electrons in TiO$_2$ monolayers, which are found to localize at a single Ti site. This induces ferromagnetism in the doped monolayers. Furthermore, charge separation between TiO$_2$ and noble metal dopants is observed which is a key parameter in influencing the selectivity and activity of photocatalytic materials. Compared to the pristine TiO$_2$ monolayer, the Janus structure can promote water adsorption, and the Janus monolayers exhibit significantly improved activity in the hydrogen evolution reaction. These findings suggest that engineering a novel Janus TiO$_2$-based monolayer with a noble metal layer on the other surface can offer a potential approach to improve photocatalytic performance over pristine TiO$_2$.