Electronic Theses and Dissertations

Date of Award


Document Type


Degree Name

Ph.D. in Chemistry


Chemistry and Biochemistry

First Advisor

Dr. Jonah Jurss

Second Advisor

Dr. Walter Cleland

Third Advisor

Dr. Jared Delcamp

Relational Format



With the increase in global population and rapid industrialization, a gigantic amount of greenhouse gases is being released into the atmosphere each year. The catastrophic effect of these accumulated greenhouse gases is driving global climate change and adversely impacting our ecosystem. Popularizing the traditional renewable energy sources (such as solar and wind energy) can mitigate the problem by cutting down anthropogenic CO2 emissions, which is the major contributor to this global problem. However, the intermittent nature of these energy sources is problematic to reliably power society throughout the year. Therefore, converting CO2 to various value-added chemicals with the aid of renewable energy sources can provide a sustainable solution by storing the energy in chemical bonds which can be used to power society, and can also give a closed carbon cycle to lower CO2 accumulation in the atmosphere. However, the main hurdle is to design suitable, robust, and inexpensive catalysts which can facilitate CO2 reduction with high efficiency and selectivity near the thermodynamic potentials of these reactions. The work presented here focuses on two different aspects of transition-metal mediated catalytic conversion of CO2 to value-added fuels. In the first part, the second-coordination sphere of well-known systems, fac-M(bpy)(CO)3X (here M = Re, Mn; and X = Cl, Br), were modified with hydrogen-bond donor groups. The effects of these functional groups on catalytic CO2 reduction relative to the parent complexes were thoroughly studied. In the latter part, isomeric anthracene-bridged dinuclear Re complexes were synthesized and studied for electrochemical and photochemical reduction of CO2. Here, the isomeric complexes were seen to catalyze electrochemical CO2 reduction by two different pathways: namely, cooperative bimetallic and single-site monometallic pathways. However, photochemically, both isomers performed similarly, suggesting that CO2 activation and reduction are achieved through the same pathway for both the complexes.


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