Electronic and structural properties of model catalysts based on cerium oxide

Catalysts based on cerium oxide are ubiquitous in industrial-scale chemical conversion. Here, a thorough study of their fundamental properties is undertaken via a model system ap- proach with the goal of furthering rational design in heterogeneous catalysis. A focus is put on understanding the behavior of oxygen vacancies in cerium oxide with respect to atomic co-ordination and electronic structure perturbations. Utilizing state-of-the-art probing tech- niques, a scalable model system framework is developed that allows for control over both the oxygen vacancy concentration and local co-ordination. High precision of the innova- tive approach facilitated observation of new phases of substoichiometric cerium oxide and lead to a first-of-a-kind investigation of the electronic structure of cerium oxide throughout isostructural transition from CeO2 to Ce2O3. The acquired results advance fundamental understanding of essential properties of cerium oxide that are relevant to its utilization in heterogeneous catalysis and open new pathways for functionalization of cerium oxide-based materials. Furthermore, the methodology developed in the thesis is transferable to other important reducible oxides.