Thesis advisor: Dunwei Wang / Atomically dispersed catalysts refer to substrate-supported heterogeneous catalysts featuring one or a few active metal atoms that are separated from one another. They represent an important class of materials ranging from single atom catalysts (SACs) and nanoparticles (NPs). The study of SACs has brought an attention of understanding the reaction mechanism at the molecular level. SACs is a promising field, however, there are still many challenges and opportunities in developing the next generation of catalysts. Catalysts featuring two atoms with well-defined structures as active sites are poorly studied. It is expected that this class of catalysts will show uniqueness in activity, selectivity, and stability. However, the difficulty in synthesizing such structures has been a critical challenge. I tackled this challenge by using a facile photochemical method to generate active metal centers consisting of two iridium metal atoms bridged by O ligands and bound to a support by stripping the ligands of the organometallic complex. My research also unveiled the structure of this dinuclear heterogeneous catalysts (DHCs) by integrating various characterization resources. Direct evidence unambiguously supporting the dinuclear nature of catalysts anchored on metal oxides is obtained by aberration-corrected scanning transmission electron microscopy. In addition, different binding modes have been achieved on two categories of metal oxides with distinguishable surface oxygen densities and interatomic distances of binding sites. Side-on bound DHCs was demonstrated on iron oxide and ceria where both Ir atoms are affixed to the surface with similar coordination environment. The binding sites on the OH-terminated surface of Fe2O3 and CeO2 anchor the catalysts to provide outstanding stability against detachment, diffusion and aggregation. The competing end-on binding mode, where only one Ir atom is attached to the substrate and the other one is dangling was observed on WO3. Evidence supporting the binding modes was obtained by in situ diffuse reflectance infrared Fourier transform spectroscopy. In addition, the synergistic effect between two adjacent Ir atoms and the uniqueness of different coordinative oxygen atoms around Ir atoms were investigated by a series of operando spectroscopy such as X-ray absorption spectroscopy and microscopy at atomic level under the reaction condition. The resulting catalysts exhibit high activities and stabilities toward H2O photo-oxidation and preferential CO oxidation. Density functional theory calculations provide additional support for atomic structure, binding sites modes on metal oxides, as well as insights into how DHCs may be beneficial for these catalytic reactions. This research has important implications for future studies of highly effective heterogeneous catalysts for complex chemical reactions. / Thesis (PhD) — Boston College, 2020. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.