Hydrophobicity Promoted Efficient Hydroxyl Radical Generation in Visible-Light-Driven Photocatalytic Oxidation

Small. 2024 Jun;20(24):e2310128. doi: 10.1002/smll.202310128. Epub 2024 Jan 4.

Abstract

Hydroxyl radical (OH) with strong oxidation capability is one of the most important reactive oxygen species. The generation of OH from superoxide radicals (O2 -) is an important process in visible-light-driven photocatalysis, but the conversion generally suffers from slow reaction kinetics. Here, a hydrophobicity promoted efficient OH generation in a visible-light-driven semiconductor-mediated photodegradation reaction is reported. Hydrophobic TiO2 that is synthesized by modifying the TiO2 surface with a thin polydimethylsiloxane (PDMS) layer and rhodamine B (RhB) are used as model semiconductors and dye molecules, respectively. The surface hydrophobicity resulted in the formation of a solid-liquid-air triphase interface microenvironment, which increased the local concentration of O2. In the meanwhile, the saturated adsorption quantity of RhB on hydrophobic TiO2 is improved by five-fold than that on untreated TiO2. These advantages increased the density of the conduction band photoelectrons and O2 - generation, and stimulated the conversion of O2 - to OH. This consequently not only increased the kinetics of the photocatalytic reaction by an order of magnitude, but also altered the oxidation route from conventional decolorization to mineralization. This study highlights the importance of surface wettability modulation in boosting OH generation in visible-light-driven photocatalysis.

Keywords: hydrophobicity; interfacial microenvironment; organic oxidation; photocatalysis; reactive oxygen species.