PhD Thesis

Nanostructures in Catalysis - Support Effects on Metal Clusters and Oxide Thin Films

PhD Thesis of Philomena Schlexer


Catalysis has largely shaped society and will play a key part in the resolution of the energy and environment crisis we are facing in this century. The great advancements in the development of nanomaterials in the realm of nanotechnology have brought forth unforeseen possibilities also for the design of novel catalysts. The production and understanding of highly efficient catalysts based on nanostructured materials is the endeavor of the emerging field of nanocatalysis. In the last years, nanocatalysts have been studied extensively and progress in their large-scale fabrication has been demonstrated. Still, the technology is immature and further research is necessary to capitalize its full potential.
Computational approaches are well suited to investigate the functioning of nanocatalysts and provide valuable atomistic insights. An accurate and efficient method is density functional theory (DFT). In this thesis, we explored the physical and chemical characteristics of supported metal clusters and oxide thin films using mainly DFT. These materials are of special interest in catalysis and many other applications, because of their unique features emerging from the nanostructuring. In particular, we investigated the geometry, the charge state, the cluster-support interaction, and the reactivity of sub-nanometer metal clusters supported on oxides. In a case study, we also addressed size-effects on larger metal nanoparticles. Regarding the supported clusters, we find that van-der-Waals dispersion forces are important for the correct description of the cluster-support interaction. Furthermore, we establish that defects and dopants present on the supporting oxide surface have a determining influence on the clusters, inherently affecting their reactivity. Also the modification of the clusters via alloying alters the metal-support interaction which can be exploited against cluster agglomeration. Nanostructuring of the oxide support engenders new material properties and in this context we examined the features of metal-supported oxide ultrathin films. Finally, we performed mechanistic studies contributing to understand the reaction mechanism of CO oxidation on Au/TiO2, as well as CO2 hydrogenation on Ru/TiO2 and Cu/TiO2.

Nanocatalysis, nanostructures, metal clusters, metal-support interaction, sintering, oxide ultrathin films, gold, silica, titania, density functional theory

PDF: Thesis

The thesis is under CC BY-NC-ND copyright.