Adsorbed metal atoms and metal doping onto TiO₂ can effectively enhance the optical and photocatalytic activity of photocatalytic efficiency of titanium dioxide (TiO₂), favoring the extension of its optical absorption spectrum and the efficiency of hydrogen generation. To investigate the possible mechanism causing potential improvement of photocatalytic activity, the electronic and optical properties of the anatase TiO₂(101) plane with different adsorbed metal atom have been theoretically calculated through density functional theory (DFT) method. Adsorption of Pd and Ru atoms increases the delocalization of the density of states, with an impurity state near the Fermi level. Moreover, the investigated adsorbed metal atoms (Mo, Pd, Ru, Rh) narrow the band gap of anatase TiO₂, thus enhancing the probability of photoactivation by visible light. The orbital hybridization of the d orbit from the adsorbed metal atom and the p orbit from the O of the defect site increases the Schottky barrier of the electronic structure.
Keywords: TiO2(101) plane; adsorption mechanism; anatase TiO2; density functional theory (DFT); electronic structure; optical absorption.