Interfacial electron transfer : the photoelectrocatalytic reduction of carbon dioxide and the reduction of hydrogen at low temperatures /
| Main Author: | |
|---|---|
| Other Authors: | , , |
| Format: | Thesis Book |
| Language: | English |
| Published: |
1989.
|
| Subjects: | |
| Online Access: | Link to OAKTrust copy |
| Abstract: | There are many unsolved problems when discussing the subject of electron transfer at interface. The work presented here addresses the problems associated with such fundamental properties of electrochemistry as the variation of β (the symmetry factor) with temperature and the lack of variation of b (the Tafel slope) with potential, which contradicts classical interpretations. The photoelectrocatalytic reduction of CO₂ at p-type semiconductor electrodes has been performed with the use of various electrocatalysts. A mechanism associated with these catalysts has been proposed to account for the observed results. The metal and metal related catalysts behave in an expected manner with the electron transfer occurring through the oxygen atom of the CO₂ molecule being reduced. The major product was CO obtained with nearly 100% current efficiency. The crown ether catalysts were found to be dependent on the size of the supporting electrolyte and adsorption properties as determined by FTIR spectroscopy. Furthermore, with the crown ether catalysts, the reduction products were as valuable as methanol. The overall current efficiency was near 100% and that for methanol was slightly greater than 10% at room temperature. Low temperature studies, down to 50 K, of the electron transfer reaction associated with hydrogen evolution were investigated on platinum and superconducting electrodes. Results indicated that the rate determining step becomes the quantum mechanical tunneling of the proton at temperatures near 100 K. Results of superconducting electrodes showed an increase of the current density which was correlated to the critical temperature, the temperature at which the superconductor becomes superconducting. This increase occurred just before the critical temperature and decreased after passing through the critical temperature back to levels before the onset of superconductivity for the electrodes investigated. This type phenomena has been accounted for by discussing how the energy gap of the superconductors reacts with temperature. |
|---|---|
| Item Description: | Typescript (photocopy). Vita. "Major subject: Chemistry." |
| Physical Description: | xx, 330 leaves : illustrations ; 29 cm |
| Bibliography: | Includes bibliographical references. |