Oxygen Vacancy Associated Surface Fenton Chemistry: Surface Structure Dependent Hydroxyl Radicals Generation and Substrate Dependent Reactivity.

Understanding the chemistry of hydrogen peroxide (HO) decomposition and hydroxyl radical (•OH) transformation on the surface molecular level is a great challenge for the application of heterogeneous Fenton system in the fields of chemistry, environmental, and life science. We report in this study a conceptual oxygen vacancy associated surface Fenton system without any metal ions leaching, exhibiting unprecedented surface chemistry based on the oxygen vacancy of electron-donor nature for heterolytic HO dissociation. By controlling the delicate surface structure of catalyst, this novel Fenton system allows the facile tuning of •OH existing form for targeted catalytic reactions with controlled reactivity and selectivity. On the model catalyst of BiOCl, the generated •OH tend to diffuse away from the (001) surface for the selective oxidation of dissolved pollutants in solution, but prefer to stay on the (010) surface, reacting with strongly adsorbed pollutants with high priority. These findings will extend the scope of Fenton catalysts via surface engineering and consolidate the fundamental theories of Fenton reactions for wide environmental applications.