Electron Transfer Reactions at Sensitized Nanocrystalline Metal Oxide Interfaces Public Deposited

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  • March 21, 2019
Creator
  • DiMarco, Brian
    • Affiliation: College of Arts and Sciences, Department of Chemistry
Abstract
  • The growing need for energy has spurred interest in the development of technologies that can directly convert solar irradiance into useful forms of energy. Dye-sensitized solar cells are a promising solar energy conversion technology due to the relatively low cost of the materials used and the tunability of the absorption profiles of the devices. The latter makes them amendable to integration into aesthetically appealing devices that can efficiently generating power. This thesis is focused on understanding the fundamentals of the electron transfer reactions that occur within these devices. The initial chapter introduces the environmental challenges facing humanity as a result of our current means of generating power. A review of the operation of a DSSCs and several important fundamental aspects are also introduced. Chapter 2 is focused on the influence that small structural changes have on the rate of electron self-exchange between ruthenium polypyridyl complexes anchored at nanocrystalline TiO2 interfaces. Chapter 3 seeks to understand the role of Lewis acidic cations during interfacial electron transfer to solution phase electron acceptors. Chapter 4 compares the rates of interfacial electron to a pair of nearly identical triphenylamine acceptors, where one of the acceptors is functionalized with a phosphonic acid functional group that allowed it to anchored to the TiO2 interface. This provided insight into the influence of surface anchoring on the recombination reaction. Chapter 5 assess the role of driving force during the recombination reaction to series of substituted triphenylamine (TPA). The substitutions afforded and ~ 0.5 V change in the TPA+/0 reduction potential, which was thought vary the driving force by the same amount. Chapter 6 compares charge recombination rates from TiO2 and SnO2 nanocrystalline thin films. Similar to Chapter 3, the role of Lewis acidic cations present in the external electrolyte was also investigated. Finally, Chapter 7 assess the role of electric fields and dipole moments on the injection and emissive properties of Ru polypyridyl complexes anchored at TiO2 interfaces.
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Rights statement
  • In Copyright
Advisor
  • Cahoon, James
  • Atkin, Joanna
  • Dempsey, Jillian
  • Miller, Alexander
  • Meyer, Gerald
Degree
  • Doctor of Philosophy
Degree granting institution
  • University of North Carolina at Chapel Hill Graduate School
Graduation year
  • 2017
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