Electron transfer kinetics in water-splitting dye-sensitized photoelectrochemical cells

Water-splitting dye-sensitized photoelectrochemical (WS-DSPECs) cells utilize molecular sensitizers absorbed on mesoporous TiO2 electrodes to harvest visible light, inject photoexcited electrons into the conduction band of TiO2, and finally transfer holes across the TiO2 surface to water oxidation catalysts, which in turn oxidize water to give molecular oxygen and four protons. Within the TiO2 layer photoinjected electrons are transported to a transparent conductor back contact and from there to a dark cathode to reduce protons to molecular hydrogen. WS-DSPECs offer several advantages for alternative solar fuels systems: the use of low-cost materials, tunable molecular sensitizers, and relaxed catalytic turnover requirements to name a few. Despite these advantageous features, power conversion efficiencies in WS-DSPECs are generally low. Broadly, this thesis explores the fundamental electron transfer processes that control the efficiency of these cells.;Chapter 1 presents a survey of the previous literature and individually considers each component of a WS-DSPEC (water oxidation catalyst, sensitizers, electrode materials, redox mediators, and overall system design). Chapter 2 presents a novel method of preparing a WS-DSPEC that utilizes crystalline IrO2 nanoparticles directly sintered to TiO2 as a water oxidation catalyst and describes a previously unknown electron-scavenging pathway by IrO2. Chapter 3 explores how electron trapping by and proton intercalation into TiO2 controls the photoelectrochemical performance of WS-DSPECs. Chapter 4 characterizes how electron recombination with the oxidized sensitizer and electron scavenging by the IrO 2 catalyst combine to limit the concentration of conduction band electrons and by extension photocurrent in WS-DSPECs. Chapter 5 demonstrates the use of the first totally organic sensitizers for light driven water-splitting and explores how the molecular and electronic structure of a sensitizer affects the electron transfer steps of injection, recombination, and hole transfer among others. Finally, in Chapter 6 a model system that describes electron transfer between an oxidized sensitizer and water oxidation catalyst is demonstrated and provides insight into sensitizer regeneration in WS-DSPECs. Together the results in these chapters present a detailed picture of how electron scavenging, recombination, and transport combine to generate photocurrent in a fully characterized WS-DSPEC and serve as starting point for the further development of WS-DSPECs.