Atomic-Scale Surface Local Structure of TiO2 and Its Influence on the Water Photooxidation Process.

The water photooxidation reaction on TiO2 and related metal oxides has been attracting strong attention from the point of view of solar water splitting. The water photooxidation reaction (i.e., oxygen evolution reaction) accompanies three other kinds of side reactions (photoluminescence (PL), surface roughening, and nonradiative recombination). These reactions are competitive with each other, and the ratio of their quantum efficiencies strongly depends on the atomic-scale surface local structure. This Perspective focuses on the atomic-scale surface local structure dependence of those four kinds of competitive reactions on a TiO2 (rutile) single-crystal electrode on which not only a terrace structure but also step structures were strictly controlled. The experimental results are discussed based on the reaction model of water photooxidation that we previously proposed. The photocatalytic activity of the TiO2 surface roughened by the photoinduced roughening process is also focused on.