Surface-Enhanced Spectroelectrochemistry using Synchrotron Infrared Radiation
Bibliographic record
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.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.003 | 0.002 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".