First-Principles Prediction of New Photocatalyst Materials with Visible-Light Absorption and Improved Charge Separation: Surface Modification of Rutile TiO₂with Nanoclusters of MgO and Ga₂O₃

Titanium dioxide is an important and widely studied photocatalytic material, but to achieve photocatalytic activity under visible-light absorption, it needs to have a narrower band gap and reduced charge carrier recombination. First-principles simulations are presented in this paper to show that heterostructures of rutil TiO₂ modified with nanoclusters of MgO and Ga₂O₃ will be new photocatalytically active materials in the UV (MgO-TiO₂) and visible (Ga₂O₃-TiO₂) regions of the solar spectrum. In particular, our investigations of a model of the excited state of the heterostructures demonstrate that upon light excitation electrons and holes can be separated onto the TiO₂ surface and the metal oxide nanocluster, which will reduce charge recombination and improve photocatalytic activity. For MgO-modified TiO₂, no significant band gap change is predicted, but for Ga₂O₃-modified TiO₂ we predict a band gap change of up to 0.6 eV, which is sufficient to induce visible light absorption. Comparisons with unmodified TiO₂ and other TiO₂-based photocatalyst structures are presented.