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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. [ABSTRACT FROM AUTHOR]

Colloidal deposition of noble metal nanoparticles on oxidic supports is a recent approach for the fabrication of heterogeneous catalyst materials. We present studies on the interaction of different amine ligands with gold nanoparticles before and after deposition on several oxidic supports (titania, silica, alumina, magnesia or zinc oxide), using X-ray photoelectron and Auger spectroscopy, and high-resolution transmission electron microscopy. The adsorption of amines on thin gold films as well as on nanoparticles leads to a decrease in metal photoelectron binding energies. Usually, this is explained by donor-acceptor interactions via the amine group. By additional analysis of Auger signals, which are more sensitive to changes in the oxidation state than photoelectron spectra, we demonstrate that these shifts are due to a final state effect, namely, the increased photoelectron hole screening in presence of amine adsorbates. It will be shown, that this effect is not sensitive neither to the nanoparticle size nor the sterical properties of the capping amine. After deposition on oxide supports, the photoelectron binding energies are even further decreased. The presented findings exhibit that care has to be taken to interpret binding energy shifts simply with charging, which has impact on understanding the local electronic situation on the surface of metal-loaded oxides, crucial for heterogeneous catalysis. [ABSTRACT FROM AUTHOR]