Electron transfer dynamics at the nanocrystalline semiconducting metal oxide interface plays a pivotal role in diverse applications such as dye-sensitized solar cells (DSSCs), dye-sensitized photoelectric solar cells (DSPECs), sensors and electrochromic thin films. Controlling intermolecular electron transfer at the interface is a critical task, capable of profoundly influencing the efficiency of these applications. Structural control via various physical and chemical design were demonstrated to effectively influence the electron transfer rates at these interfaces. Of these approaches, in situ molecular assembly has emerged as an appealing strategy due to the simple preparation to form complex rigid structure that traditionally requires design of one large molecule elaborated with multiple components. In molecular assembly, molecules are adhered to a nanocrystalline metal oxide surface utilizing similar binding motifs and molecular structure-property relationships at the interface to achieve disparate electron transfer dynamics outcomes. In this dissertation, we demonstrated the use of self-assembled bilayer as a scaffold to influence the interfacial electron transfer rates to further our goal of enhancing the productive kinetics while inhibiting the unproductive pathways. By utilizing self-assembled bilayers, we achieved electron transfer modulation while preserving the individual molecule’s electronic structure and property. Chapter 1 is an introductory chapter that lays the foundation of operation principles of DSSCs, electron transfer events at the photoanode, and the physical parameters that govern these processes. Notably, the importance of molecular structural control and a brief history of past approaches are introduced at the end of Chapter 1 as an inspiration for self-assembled bilayers. The remaining chapters take deeper dives into different strategies of varying individual components’ electrochemical properties in order to influence the overall physical properties of the film. We modified the chemical structure of the bridging molecules to influence the electron tunneling rate. For example, Chapters 2 and 3 explore the effect on the electron transfer rate of tuning the distance and energy parameters of bridge molecules by employing self-assembled bilayers. Various properties of the bilayer structure are examined in Chapter 4 and 5, which describe the fundamental studies we have done to investigate role of metal liking ions in the self-assembled bilayers. Together the results in these chapters present an architectural alternative for supramolecular assembly designed to influence electron transfer dynamics in a fully functioning DSSC, and it serves as a foundation for future development of DSSC design. / A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy. / Spring Semester 2018. / April 2, 2018. / Includes bibliographical references. / Kenneth Hanson, Professor Directing Dissertation; Zhiyong Liang, University Representative; Michael Roper, Committee Member; Joseph B. Schlenoff, Committee Member.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_653525 |
| Contributors | Wang, Jamie Chieh-Ming (author), Hanson, Kenneth G. (professor directing dissertation), Liang, Zhiyong (university representative), Roper, Michael Gabriel (committee member), Schlenoff, Joseph B. (committee member), Florida State University (degree granting institution), College of Arts and Sciences (degree granting college), Department of Chemistry and Biochemistry (degree granting departmentdgg) |
| Publisher | Florida State University |
| Source Sets | Florida State University |
| Language | English, English |
| Detected Language | English |
| Type | Text, text, doctoral thesis |
| Format | 1 online resource (162 pages), computer, application/pdf |
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