Catalysis is one of the most important technical and scientific developments, on which present-day society is based. For example, it is crucial to the production of fertilizers or clean... Show more Catalysis is one of the most important technical and scientific developments, on which present-day society is based. For example, it is crucial to the production of fertilizers or clean fuels and needed for the abatement of exhaust gases. Frequently, the employed catalysts are being discovered in a very empirical way; by trial and error. However, designing catalysts based on detailed understanding is preferred. Obtaining understanding is very difficult, because catalysts are very complex materials. Furthermore, its properties often depend on the atmosphere surrounding the catalysts, i.e., the temperature and pressure of reactants and products, which they are exposed to, and these properties also change over time. The major part of this thesis focuses on structural changes of Pt model catalysts exposed to high oxygen pressures at elevated temperatures. The changes were measured with a ReactorSTM, a special version of a scanning tunneling microscope (STM) adapted to operate at high pressure and temperatures. These observations show that various surface oxide with a single-layer thickness form under reaction conditions. These oxides are structurally and chemically different from the Pt bulk oxides. The second part describes a set of experiments to understand the role of low-coordinated atoms and water in Au-catalyzed CO oxidation. Show less
This thesis describes the development of a combined high-pressure/ultrahigh-vacuum flow reactor for the study of model catalysts by means of surface x-ray diffraction and grazing incidence small... Show moreThis thesis describes the development of a combined high-pressure/ultrahigh-vacuum flow reactor for the study of model catalysts by means of surface x-ray diffraction and grazing incidence small angle scattering. The system was used to measure a stability diagram for the different oxide phases (surface oxide, bulk-like oxides) that exist on Pd(100) during catalytic CO oxidation at near ambient pressures. As soon as an oxide was present the reactivity of the surface was found to be mass transfer limited by the flux of CO molecules reaching the surface. Experiments on spontaneous reaction oscillations of the CO oxidation rate on Pd(100) reveal that a high density of steps strongly alters the stability of the thin, catalytically active palladium oxide film. It is shown that stabilization of the metal, caused by the steps and consequent destabilization of the oxide, is at the heart of the well-known reaction rate oscillations exhibited during CO oxidation at atmospheric pressure. Lastly reaction oscillations on supported Pd nanoparticles are shown to be accompanied by shape changes of the particles consistent with the formation and removal of a thin palladium oxide film on the particles. Show less
This thesis describes the construction of a second generation high-pressure, high-temperature scanning tunneling microscope, the ReactorSTM, with which the surfaces of catalysts can be studied... Show moreThis thesis describes the construction of a second generation high-pressure, high-temperature scanning tunneling microscope, the ReactorSTM, with which the surfaces of catalysts can be studied under relevant reaction conditions. Furthermore, the thesis describes three separate catalytic systems at ~ 1 bar, and elevated temperatures. Firstly, NO reduction on Pt(100), in which a mathematical model for the reaction mechanism, following Langmuir-Hinshelwood kinetics, is proposed. Secondly, CO oxidation, in which the Pt(110) surface is atomically resolved at high p, T. Thirdly, the thesis describes a successful pilot experiment about the hydrodesulphurization of thiophene, which is catalytically activated by molybdenum disulphide nano-crystallites on an Au(111) support. Show less
