Controlling Electron Transfer Photoreactivity of Ruthenium Polypyridyl Compounds at the Semiconductor Interface and in Solution Public Deposited

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  • March 20, 2019
Creator
  • Beauvilliers, Evan
    • Affiliation: College of Arts and Sciences, Department of Chemistry
Abstract
  • The herein described work is motivated by the need to develop renewable energy sources. Given the magnitude of the growing global energy demand, solar energy will undoubtedly comprise a significant component of future renewable energy generation, necessitating the development of cheaper, more efficient solar technologies. Towards this end, this work describes the study of electron transfer reactions relevant to dye-sensitized solar cells (DSSCs). Chapters 2 & 3 focus on electron transfer reactions at the semiconductor interface. Chapter 2 presents the study and simulation of intra- and intermolecular electron transfer reactions that may be useful for transporting charges to catalytic reaction centers for fuel production or for the design of new types of solid state DSSCs utilizing such charge transport mechanisms for sensitizer regeneration. Chapter 3 describes work in developing new types of sensitizer-semiconductor linkages to improve interfacial electron transfer kinetics, which is of critical importance for improving device efficiency. A new sensitizer is presented that has improved interfacial kinetics relative to a structurally similar compound bearing one of the “standard” semiconductor linkages. The remaining chapters of this work study and utilize secondary coordination sphere interactions to manipulate the excited-state reactivity of molecular sensitizers. In Chapter 4, an iodide binding pocket is utilized to ion-pair an iodide ion with an excited state, and it is shown that the ion-paired iodide does not quench this excited state, but rather this excited state is quenched by a second iodide in solution. Such a mechanism may be useful in trying to access a concerted mechanism for iodide oxidation and I-I bond formation. Chapter 5 presents the study of Lewis acid-base interaction between carboxylates on sensitizers and metal cations in acetonitrile solutions. These interactions are shown to tune the photophysical properties of the sensitizers in a predictable way, and are furthermore shown to mediate excited-state electron transfer between sensitizers that do not undergo electron transfer in the absence of the cations.
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  • In Copyright
Advisor
  • Miller, Alexander
  • Cahoon, James
  • Meyer, Gerald
  • Dempsey, Jillian
  • Papanikolas, John
Degree
  • Doctor of Philosophy
Degree granting institution
  • University of North Carolina at Chapel Hill Graduate School
Graduation year
  • 2017
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