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Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a sig- nificant substrate-mediated interaction between adsorbates. The result is a complex super- structure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not depro- tonate on the defect-free terraces of the rutile TiO2(110) surface.
For this study gas diffusion electrodes (GDE) with low platinum loading are prepared for the application as anode in polymer electrolyte membrane fuel cell (PEMFC) systems based on hydraulic compression. As catalyst support material, carbon nanofibers (CNF) are investigated because of their high specific surface area and high graphitization degree. The electrode preparation is optimized by an economic and environmental friendly pre-treatment process in oxygen plasma. For GDE manufacture an ink containing oxygen plasma activated CNFs as well as hydrophilic polymer is used. After spray coating of this CNF ink on a graphitic substrate, platinum is deposited using the pulse plating technique. Preliminary results showed a considerable improvement of CNF dispersibility as well as an increased amount and an optimized morphology of the deposited platinum. Morphology and microstructure are observed by scanning electron microscopy as well as transmission electron microscopy. Platinum loading is determined by thermogravimetric analysis to be in the range of 0.01 mg cm-2 to 0.017 mg cm-2. Furthermore, MEAs are prepared from these GDEs and testing is performed in a novel modular fuel cell test stack based on hydraulic compression. Technical information about stack design and functions is given in this work.