Electronic Theses and Dissertations

Date of Award

1-1-2022

Document Type

Dissertation

Degree Name

Ph.D. in Chemistry

First Advisor

Jared H. Delcamp

Second Advisor

Nathan I. Hammer

Third Advisor

Jonah W. Jurss

School

University of Mississippi

Relational Format

dissertation/thesis

Abstract

Solar energy technologies, such as dye-sensitized solar cells (DSCs) and photoelectrochemical cells (PECs), rely on electron transfer reactions to convert light waves from the Sun to usable electrical energy. These electron transfers are vital to the performance of solar energy technologies. However, two main unproductive electron transfers (recombination and back electron transfer) are possible in these systems, making it vital to study and increase the efficiency of the beneficial electron transfers while hindering the possibility of unproductive pathways from occurring. Through modulation of the organic chromophore/dye used in DSCs, lower recombination rates, and back electron transfer rates are afforded. Three approaches are utilized in this work: varying the number of bulky alkyl chains, increasing the bond angle of the π-bridge spacer unit by using methyl groups, and accessing the Marcus inverted region by lowering the highest occupied molecular orbital (HOMO) using withdrawing groups on the donor of the dye. These approaches yielded various results, including a champion strong photooxidant dye, RR9, controlling recombination and producing a 1.4 V high voltage (HV) DSC device, a lowered rate of back electron transfer by 22x by dye CC10, and accessing the Marcus inverted region leading to lowered rates of recombination through the use of the energetically record-breaking HV dye, QL14.

Available for download on Friday, January 30, 2026

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