Chemistry ETDs

Publication Date



CO2 reduction is a pressing problem worldwide, and one obstacle in the electrochemical conversion of CO2 to more useful C1 products such as methanol and formic acid is the kinetic barrier known as overpotential. The overpotential of rearranging the nuclei in CO2 to accommodate electron transfer can be lowered by pre-bending the CO2 molecule in an adduct-mediated complex. The work presented in Part I utilizes a combination of hard and soft donors on pincer-like ligands to effect the bending of CO2 prior to electrochemical reduction. A large majority of the work consists of using Group 4 metallocenes, but Chapter 3 outlines Zn-based compounds that also show promise in the reduction of CO2. A refined methodology has been employed to increase the yield of the ligand 2-di-tert-butylphosphinophenol. Previous literature preparations could only accommodate approximately 1 g of product per batch, but by using the methodology found in this dissertation, the ligand can now be synthesized in large batches (>15 g). 2-diisopropylphosphinothiophenol and 2-diphenyl-phosphinothiophenol were synthesized for the first time by our group, and their utility was explored in relation to Group 4 metallocenes. The work presented in Part II of this dissertation illustrates the usefulness of homogenous electrochemical interactions in space-based applications. New ventures toward reversible electrochemical mirror (REM) technology were explored using silver and copper cations solvated between two transparent conductive films. Silver deposited upon these conductive thin films to produce seamless mirrors, and by controlling silver nanoparticle growth clusters with ramping voltages, thin colored films were also deposited.

Project Sponsors

National Science Foundation, Universities Space Research Association, Air Force Research Laboratory




CO2 Reduction, Carbon Dioxide, Greenhouse gas, electrochemistry, reversible mirrors

Document Type


Degree Name


Level of Degree


Department Name

Department of Chemistry and Chemical Biology

First Advisor

Kemp, Richard

First Committee Member (Chair)

Kirk, Martin

Second Committee Member

Giri, Ramesh

Third Committee Member

Sharp, Zachary