| Direct solar--to--fuels conversion can be achieved by coupling semiconductors with water--splitting catalysts. A 10% or higher solar to fuels conversion is minimally necessary for the realization of a robust future technology. Many water--splitting devices have been proposed but due to expensive designs and/or materials, none have demonstrated the necessary efficiency at low--cost that is a requisite for large--scale implementation. In this thesis, a modular approach is used to couple water--splitting catalysts with crystalline silicon (c--Si) photovoltaics, with ultimate goal of demonstrating a stand--alone and direct solar-to-fuels water--splitting device comprising all non--precious, technology ready, materials.;Since the oxygen evolution reaction is the key efficiency--limiting step for water--splitting, we first focus on directly interfacing oxygen evolution catalysts with c--Si photovoltaics. Due to the instability of silicon under oxidizing conditions, a protective interface between the PV and OER catalyst is required. This coupling of catalyst to Si semiconductor thus requires optimization of two interfaces: the silicon|protective layer interface; and, the protective layer|catalyst interface. A modular approach allows for the independent optimization and analysis of these two interfaces.;A stand--alone water--splitting device based on c--Si is created by connecting multiple single junction c-Si solar cells in series. Steady--state equivalent circuit analysis allows for a targeted solar--to--fuels efficiency to be designed within a predictive framework for a series--connected c--Si solar cells and earth--abundant water--splitting catalysts operating at neutral pH. Guided by simulation and modeling, a completely modular, stand--alone water--splitting device possessing a 10% SFE is demonstrated. Importantly, the modular approach enables facile characterization and trouble--shooting for each component of the solar water--splitting device. Finally, as direct solar water--splitting is far from a mature technology, alternative concepts are presented for the future design and integration of solar water--splitting devices based on all earth--abundant materials. |
