Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons.

Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

Local density of states effects at the metal-molecule interfaces in a molecular device.

Clarifying the nature of interactions between metal electrodes and organic molecules still represent one of the challenging problems in molecular electronics that needs to be solved in order to optimize electron transport through a molecular device. For this purpose, electronic properties at metal-molecule interfaces were studied by combining experimental and theoretical methods. Applying a novel electrochemical approach, strictly two-dimensional Pd islands were prepared on top of 4-mercaptopyridine self-assembled monolayers (4MP-SAMs) which, in turn, were deposited on (111)-oriented Au single crystals. Electron spectroscopy together with density functional theory calculations revealed strong interactions between the molecules and the islands due to Pd-N bonds, resulting in a drastically reduced density of states (DOS) at the Fermi level EF for a nearly closed Pd monolayer, and even non-metallic properties for nanometre-sized islands. Similarly, a significantly reduced DOS at EF was observed for the topmost Au layer at the Au-SAM interface due to Au-S interactions, suggesting that these effects are rather general.