Role of four-fold coordinated titanium and quantum confinement in CO2 reduction at titania surface

Photocatalytic reduction of carbon dioxide (CO(2)) into hydrocarbons is an attractive approach for mitigating CO(2) emission and generating useful fuels at the same time. Titania (TiO(2)) is one of the most promising photocatalysts for this purpose, and nanostructured TiO(2) materials often lead to an increased efficiency for the photocatalytic reactions. However, what aspects of and how such nanomaterials play the important role in the improved efficiency are yet to be understood. Using first-principles calculations, reaction mechanisms on the surface of bulk anatase TiO(2)(101) and of a small TiO(2) nanocluster were investigated to elucidate the role of four-fold coordinated titanium atoms and quantum confinement (QC) in the CO(2) reduction. Significant barrier reduction observed on the nanocluster surface is discussed in terms of how the under-coordinated titanium atoms and QC influence CO(2) reduction kinetics at surface. It is shown that the reduction to CO can be greatly facilitated by the under-coordinated titanium atoms, and they also make CO(2) anion formation favorable at surfaces.