Spontaneous Production of Ultrastable Reactive Oxygen Species on Titanium Oxide Surfaces Modified with Organic Ligands

The spontaneous formation and long-term surface stabilization of superoxide radicals are observed on specific TiO2 hybrid materials in which titanium is coordinated to an organic ligand. Here the rationale for this uncommon phenomenon investigated by a synergistic theoretical experimental approach involving density functional theory (DFT) calculations spectroscopic techniques. Stoichiometric reduced anatase (101) surfaces modified with acetylacetone, dibenzoylmethane, catechol comparatively examined. These results reveal that interaction between ligands adsorbed O2 molecules improves when O vacancies present external layer surface, promoting reduction. electronic features ligand play pivotal role both effective generated reactive oxygen species. agree data showing sol–gel-derived Ti-diketonate oxides spontaneously produce very persistent under ambient conditions, thus holding high intrinsic oxidative activity.