Activation of Small Organic Molecules on Ti²⁺-Rich TiO₂ Surfaces: Deoxygenation vs. C–C Coupling

Abstract Rutile TiO2 is an important model system for understanding the adsorption and conversion of molecules on transition metal oxide catalysts. In the last decades, point defects, such as oxygen vacancies and Ti3+ interstitials, exhibited an important influence on the reaction of oxygen and oxygen-containing molecules on titania surfaces. In brief, partially reduced TiO2 containing a significant amount of Ti3+ is often more active for the conversion of such molecules. In this study, we investigate an even higher reduced surface prepared by argon ion bombardment of a rutile TiO2 (110) single crystal. By X-ray photoelectron spectroscopy we show that, besides Ti4+, this surface is almost equally dominated by Ti3+ and Ti2+. To probe the reactivity of these highly reduced surfaces, we have adsorbed two different classes of oxygen-containing molecules and utilized temperature programmed reaction spectroscopy to investigate the conversion. While alcohols (in this case methanol) already show a defect-dependent partial conversion in a deoxygenation reaction on the (stochiometric or slightly reduced) rutile TiO2 (110) surface, ketones (e.g. acetone) are usually not converted on the rutile TiO2 (110) surface independent on the bulk defect density. Here, we present a nearly full conversion for both molecules via deoxygenation reactions and reductive C–C coupling, forming different hydrocarbons at different temperatures between 375 K and 640 K on the sputtered Ti2+ rich surface.