Date Awarded

Summer 2021

Document Type

Thesis

Degree Name

Master of Science (M.Sc.)

Department

Chemistry

Advisor

William R McNamara

Committee Member

Christopher J Abelt

Committee Member

Robert D Pike

Abstract

Artificial Photosynthesis (AP) focuses on developing methods for the conversion of solar energy into chemical fuel in the form of H2 and O2. Heterogeneous photocatalytic systems incorporating carbon nanotubes (CNTs) have shown much promise but are currently limited and expensive due to their reliance on noble metals. To that end, this work focuses on the development and synthesis of cheaper naphthalene- and pyrene-terminated iron polypyridyl complexes for use in the simultaneous functionalization of carbon surfaces, electrocatalytic proton reduction, and eventual incorporation in photocatalytic systems. Cyclic voltammetry was used to characterize the adsorption behavior of each complex on the surface of a glassy carbon electrode. For the naphthalene variant, electrode-surface adsorption saturation was reached after 720 minutes with a maximum surface coverage of 7.7*10-11 mol/cm2, and the complex was found to be relatively surface-stable in solvents lacking hydrogen-bond donors or acceptors. Upon the addition of TFA, proton reduction catalysis occurred at -1.13 V vs. SCE in CH3CN with an overpotential of 480 mV. Additionally, the surface adsorbed naphthalene-functionalized complex was found to be active for hydrogen generation from purely aqueous buffer solutions of pH = 3.8 – 6.2. A pyrene variant was synthesized through a palladium-catalyzed amination. Its maximum surface coverage on a glassy carbon electrode was found to be 3.9*10-11mol/cm2. The complex was found to be a weak electrocatalyst for proton reduction, with proton reduction catalysis occurring at -1.00 V vs. SCE upon the addition of TFA.

DOI

http://dx.doi.org/10.21220/s2-6z54-np26

Rights

© The Author

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