Defense Date


Document Type


Degree Name

Doctor of Philosophy



First Advisor

Shiv N. Khanna


First principles theoretical studies based on a gradient-corrected density functional approach have been carried out on the atomic and electronic properties and oxidation of Pdn (n=1-7) clusters supported on the TiO2(110) surface. The studies are aimed to address some of the fundamental issues related to the properties of supported Pdn clusters used as catalysts in oxidation reactions. Of those issues are the following: What are the atomic structures of Pdn clusters on the TiO2 surface? Upon oxidation, do O atoms from a dissociated O2 molecule spill over onto the underlying TiO2 sup- port? How strongly does spillover oxygen bind? What is the microscopic mechanism for the experimentally observed strong metal support interaction (SMSI) state where the Pd catalyst becomes encapsulated by the surface? Is this related to spillover oxygen? How do the properties of the Pdn clusters change when the TiO2 surface is marked with oxygen vacancies? As will be shown, the ground state geometries of supported Pdn clusters are driven by competing effects including intra-cluster interactions favoring compact structures and cluster support interactions favoring geometries that flatten out in the TiO2(110) surface channel. When exposed to O2, a single Pd atom only activates the O-O bond while all other clusters energetically favor a broken O-O bond. For PdnO2 (n=2-7), while one O is adsorbed on the Pdn cluster, the second O spills over to a lattice Ti site binding at the Pd-Ti interface. The binding strength of these spillover atoms is calculated to be surprisingly high, which is identified to be a result of long-range ionic interactions between Pd and spilled over oxygen. When oxygen spills onto lattice Ti sites, composite TiO motifs are formed that can exchange sites with Pd atoms with a minimal energy, opening the pathway for Ti migration and strong metal support interactions. For the TiO2 surface with oxygen vacancies, clusters bound at the vacancy site possess atomic and electronic properties that resemble bulk palladium. The theoretical findings are compared with recent experiments and are believed to provide insight toward developing a fundamental understanding of supported Pdn clusters as oxidation catalysts.


© The Author

Is Part Of

VCU University Archives

Is Part Of

VCU Theses and Dissertations

Date of Submission

December 2011


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