Crystal phase-dependent generation of mobile OH radicals on TiO2: Revisiting the photocatalytic oxidation mechanism of anatase and rutile

Titanium dioxide has been the most popular environmental photocatalyst of which role critically depends on the generation of OH radicals. In particular, the mobile free OH racial ((OHf)-O-center dot) generation and the subsequent diffusion from the surface are critical in achieving the mineralization of non-adsorbing substrates by extending the reaction zone from the surface to the solution bulk. Here the origin of the crystalline phase-dependent generation of (OHf)-O-center dot was investigated using tetramethylammonium (TMA) cation as a main probe compound for (OHf)-O-center dot in a UV/TiO2 photocatalytic system. We found a clear evidence that the mobile free OH radical is generated through a reductive conversion of dissolved O-2 on anatase only (O-2 -> H2O2 -> (OHf)-O-center dot. The surface trapped holes are not involved in (OHf)-O-center dot formation, but lead to the generation of surface-bound OH radical ((OHs)-O-center dot) on both anatase and rutile. The generation of (OHf)-O-center dot is favorable on anatase because more H2O2 are evolved (via dioxygen reduction) and adsorbed on the anatase surface. Rutile showed little sign of (OHf)-O-center dot formation. The generation of O-18-labelled p-hydroxybenzoic acid on anatase only (not rutile) from benzoic acid oxidation under O-18(2)-saturated condition provides a solid evidence that the (OHf)-O-center dot generation mechanism on anatase involves the reductive pathway. Better understanding of (OHf)-O-center dot production pathway in photocatalysis will provide a new insight leading to an engineering solution for how the production of (OHf)-O-center dot can be maximized, which is critically important in achieving the efficient photocatalytic oxidation of various pollutants.

Automated summary

The generation of mobile free OH radicals on anatase through a reductive conversion of dissolved O2 is crucial in achieving the mineralization of non-adsorbing substrates, while surface trapped holes lead to the generation of surface-bound OH radicals on both anatase and rutile. Understanding the production pathway of OH radicals in photocatalysis will help optimize their generation for efficient photocatalytic oxidation of pollutants.