Date of Award
Master of Arts
Dr. John E. Chateauneuf
Dr. John B. Miller
Dr. Marc W. Perkovic
Masters Thesis-Open Access
Recent research interest on supercritical CO2 includes the following three important issues: 1) the development of supercritical CO2 as an environmental benign reaction medium and as a viable alternative to hazardous organic solvents, 2) the use of supercritical CO2 as a C1 feedstock for fixation of CO2 and 3) characterization of photoinduced electron transfer reactions under supercritical conditions.
The reductive photocarboxylation of aromatic hydrocarbons such as anthracene and phenanthrene in supercritical CO2, have been chosen for study. Supercritical CO2 was utilized as both a replacement solvent and as a reacting reagent for the formation of carbon-carbon bonds and addition of a functional group. By comparison with similar reactions in regular organic solvents, photocarboxylation in supercritical CO2 has higher yield and selectivity. This fundamental study helped to understand the influence of supercritical CO2 as a solvent and its influence on photocarboxylation reactions. The mechanistic investigation combined with time-resolved laser flash photolysis and other spectroscopic methods, shows that carboanion radical intermediates are involved in this photoinduced electron transfer process.
Zhang, "Reductive Photocarboxylation of Aromatic Hydrocarbons in Supercritical CO2: A Mechanistic Investigation" (2000). Master's Theses. 4265.