Surface-Enhanced Spectroelectrochemistry using Synchrotron Infrared Radiation
| dc.contributor.advisor | Burgess, Ian J. | |
| dc.contributor.committeeMember | Mueller, Jens | |
| dc.contributor.committeeMember | Ellis, Thomas | |
| dc.contributor.committeeMember | Kelly, Timothy | |
| dc.creator | Morhart, Tyler | |
| dc.date.accessioned | 2021-09-28T13:20:58Z | |
| dc.date.available | 2021-09-28T13:20:58Z | |
| dc.date.created | 2021-09 | |
| dc.date.issued | 2021-09-28 | |
| dc.date.submitted | September 2021 | |
| dc.date.updated | 2021-09-28T13:20:58Z | |
| dc.description.abstract | Electrochemical reactions are inherently heterogeneous, occurring at the interface between a solid electrode and an electrolyte solution. Therefore, detailed mechanistic understanding requires the electrode/solution interface (ESI) to be interrogated. Doing so with spectroelectrochemical techniques generally encounters several analytical challenges. Sampling the ESI requires a surface-sensitive spectroscopy capable of addressing a buried interface, placing strong limitations on photon energy and spectroelectrochemical cell design. Furthermore, dynamic measurements are fundamentally limited by the finite rise time of the electrode. For many important processes with characteristic timescales in the milli- to microsecond regime, achieving a suitably low rise time requires the use of an electrode with critical dimensions in the hundreds of micrometers, i.e. a microelectrode. In this thesis, I develop the spectroscopic platform necessary to perform surface-sensitive, time-resolved infrared measurements in the milli- to microsecond regime. I will make the case that an infrared spectroelectrochemical technique, namely attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), is applicable because it is intrinsically surface-sensitive, yields detailed information on molecular structure, and is compatible with a range of electrocatalytic metals. I will show that the small size of the microelectrode requires an unconventional infrared source, namely highly focused synchrotron radiation. This thesis will present the characterization of a new internal reflection element which is fully compatible with ATR-SEIRAS and easily amenable to microfabrication. A custom horizontal microscope endstation will be developed at the mid-IR beamline at the Canadian Light Source. Its general utility beyond the primary goal of this thesis will be demonstrated with imaging experiments of a simple interfacial reaction in a microfluidic device. Finally, a 500 micrometer wide linear microelectrode compatible with ATR-SEIRAS will be fabricated and preliminary kinetic measurements of a model electrochemical process, namely the potential-induced desorption of 4-methoxypyridine, will be discussed. | |
| dc.format.mimetype | application/pdf | |
| dc.identifier.uri | https://hdl.handle.net/10388/13617 | |
| dc.subject | ATR-SEIRAS | |
| dc.subject | synchrotron infrared radiation | |
| dc.subject | microfabrication | |
| dc.title | Surface-Enhanced Spectroelectrochemistry using Synchrotron Infrared Radiation | |
| dc.type | Thesis | |
| dc.type.material | text | |
| thesis.degree.department | Chemistry | |
| thesis.degree.discipline | Chemistry | |
| thesis.degree.grantor | University of Saskatchewan | |
| thesis.degree.level | Doctoral | |
| thesis.degree.name | Doctor of Philosophy (Ph.D.) |