In the development of renewable energies catalysis plays an important role, for example in the production of H₂ gas that drives fuel cells, or in the decomposition of annoying by-products of renewable energy production. Most catalysts and catalytic processes currently used in the industry have their roots in macroscopic empirical investigations and trial and error-based optimization. In order to be able to design novel catalytic processes more efficiently, detailed understanding of the catalyst-reactant interaction and the dynamics of the microscopic reaction steps is needed. The present thesis aims to contribute to the fundamental understanding of catalyst reactant systems by means of experiments using model systems in Ultra High Vacuum. For this purpose, several surface science techniques were employed such as vibrational sum-frequency generation (SFG), X-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD) and femtochemistry.

In the present thesis the results of three different projects are presented. The first concerns the adsorption and decomposition of naphthalene on Ni(111). Using scanning tunnelling microscopy (STM) and density functional theory (DFT) we identify the adsorption energy and geometry of the naphthalene molecule. Using SFG and TPD we investigate the temperature dependent breakdown of the naphthalene molecule and identify geometrical changes of the adsorbate as an intermediate step in the decomposition reaction. Additionally, we observe poisoning of the surface due to graphene growth using both STM and XPS and explore the possible effect of co-adsorption with oxygen on the reaction pathway and the poisoning of the catalyst.

The second section concerns the adsorption and decomposition of ethanol and methanol on cuprous oxide (Cu₂O). Using mainly XPS and SFG we show that ethanol adsorbs dissociatively on Cu₂O(100) and (111) and that methanol adsorbs dissociatively on the (100) but molecularly on the (111) surface. Furthermore, we identify intermediate surface species and products of the temperature dependent dehydrogenation of both alcohols and show that the (111) surface is the more effective catalyst for decomposition.

The third section explores the physics of non-thermal excitation methods and discusses CO oxidation on ruthenium (0001) induced by an optical laser and by X-rays from a free electron laser. Based on these femtochemistry experiments we discuss in particular the energy transfer both for direct excitation and for substrate mediated excitations. We show that we were able to control the branching ratios of competing mechanisms and understand the role of non-thermal electrons in the mechanisms of optical laser excitation. Furthermore, we show that it is possible to induce CO oxidation by direct X-ray core hole excitation and can rationalize the relaxation process that leads to CO oxidation.