Origin and Electronic Features of Reactive Oxygen Species at Hybrid Zirconia-Acetylacetonate Interfaces

Abstract

The hybrid sol-gel zirconia-acetylacetonate amorphous material (HSGZ) shows high catalytic activity in oxidative degradation reactions without light or thermal pretreatment. This peculiar HSGZ ability derives from the generation of highly reactive oxygen radical species (ROS) upon exposure to air at room conditions. We disclose the origin of such unique feature by combining EPR and DRUV measurements with first-principles calculations. The organic ligand acetylacetonate (acac) plays a pivotal role in generating and stabilizing the superoxide radical species at the HSGZ-air interfaces. Our results lead the path toward further development of HSGZ and related hybrid materials for ROS-based energy and environmental applications.

Keywords: DFT; EPR; ROS; acetylacetonate complex; hybrid organic−inorganic material; zirconia.