Thesis advisor: Udayan Mohanty / Among the existing strategies to direct solar energy harvesting and storage, solar fuel production by photoelectrocatalysis promises a comparatively simple, low-cost route. The science behind this process is straightforward: stable semiconductors absorb sunlight and use the energy to excite charges, which then drive redox reactions at the surface. Careful studies of the photoelectrode surface provide important considerations in building a high-performance photoelectrode. Specifically, I focused on controlling the surface band alignment of Cu2O photocathode|water for hydrogen evolution reaction. A ZnS buried heterojunction is formed to improve the photovoltage. Then I focused on understanding the influence of chemical species on surface kinetics and energetics for water oxidation reaction. Two hematite photoanodes with preferably exposed {001} and {012} facets were examined. Further, I systematically studied three different types of surfaces, bare hematite, hematite with a heterogenized Ir water oxidation catalyst (WOC), and a heterogeneous IrOx WOC. While both WOCs improve the performance of hematite by a large margin, their working mechanisms are found to be fundamentally different. I also focused on utilizing surface photoexcited species to control product selectivity. Selective CO production by photoelectrochemical methane oxidation is successfully demonstrated. Detailed experimental investigations revealed that a synergistic effect by adjacent Ti3+ sites is the key to CO formation. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.