Understanding the Limitations of Photoelectrochemical Water Splitting

Abstract

Artificial photosynthesis is achieved by placing a semiconductor in water, where photoexcited charges generate a photovoltage at the surface of the semiconductor. However, solar to fuel efficiencies of earth abundant metal oxides and metal nitrides remain limited by their low photovoltages. Many different treatments have been used to improve the photovoltages of semiconductors, such as photocharging, surface regrowths, or the addition of heterogeneous catalysts. However, in these treatments, it remains unclear whether the enhanced photovoltage arises from improved kinetics or energetics. In many of the following studies, the surface kinetics of different semiconductors are measured in order to quantify how surface kinetics are related to the photovoltage of these materials. Different spectroscopic measurements are made along with detailed analysis of the Fermi level and quasi Fermi level in order to corroborate the kinetic data with energetic data. Together, this dissertation explores a multitude of methods and procedures that demonstrate how the photovoltage of semiconductors can be understood and manipulated for photoelectrochemial artificial photosynthesis.