Electronic Theses and Dissertations

Date of Award

1-1-2015

Document Type

Dissertation

Degree Name

Ph.D. in Chemistry

Department

Chemistry and Biochemistry

First Advisor

Jared H. Delcamp

Second Advisor

John M. Rimoldi

Third Advisor

Amala Dass

Relational Format

dissertation/thesis

Abstract

One of the most important questions humanity will face in the next 100 years is going to be "What will happen when oil runs out?" This dissertation describes efforts to utilize solar energy to improve renewable energy technology in two ways: First, through the improvement of dye sensitized solar cells by theimprovement of D-π-A dye subunits, the development of practical sensitizers, and progress towards stable, tunable redox shuttles. A novel indolizine donor subunit was synthesized that was shown to be the strongest reported donor. Dyes made from this novel donor and devices using the Γ-/I 3- reached up to 5.4% efficiency. This donor was then systematically improved by the addition of non-conjugated substituents, which acted as good surface blocking groups and thus facilitated high performance during device testing. Dyes made using this donor and devices using the Γ-/I 3- redox shuttle reached up to 6.7% efficiency. Second, this thesis describes efforts to close the carbon cycle through utilization of solar energy in CO2 reduction. The described efforts regard the improvement of known catalysts through increased stability and performance, and of the use of a simulated solar spectrum to improve the practicality of photocatalyticCO2 reduction. By the substitution of a pyridyl chelating group for an N-Heterocyclic Carbene (NHC) ligand, the synthesized complexes were more stable while still absorbing visible light. The synthesized complexes operated as photocatalysts with or without a photosensitizer, making this the fourth reported series ofnon-sensitized photocatalysts for CO2 reduction.

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