Radiotracers and NMR as in situ probes at the electrochemical interface
Chan, Kyle W.H.
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https://hdl.handle.net/2142/19714
Description
Title
Radiotracers and NMR as in situ probes at the electrochemical interface
Author(s)
Chan, Kyle W.H.
Issue Date
1991
Doctoral Committee Chair(s)
Wieckowski, Andrzej
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Analytical
Chemistry, Physical
Language
eng
Abstract
The design and construction of a radiotracer instrument which allows the quantitative measurement of a radiolabeled adsorbate on atomically smooth electrodes for the first time is described. Using this instrument, the surface mobilities of three organic molecules (pyridine, formic acid, and acetic acid) adsorbed on polycrystalline Pt electrodes were found to be inversely proportional to their strength of adsorption.
Using $\sp{13}$C spin-echo NMR a signal from 99% $\sp{13}$C enriched methanol adsorbed onto Pt black was obtained which has a chemical shift of $\sim$375 ppm. T$\sb1$ for the adsorbate was found to be between 100 and 200 msec. T$\sb2$ is believed to be on the order of ten's of $\mu$sec and increases with the age of the sample. A unique additional carbon signal at $-$14 ppm was observed to grow with time for a few months and then stabilized. The linewidth of the peak suggests that it may be a solution species while the T$\sb1$, being very short, is indicative of attachment to a source of conduction electrons such as a Pt surface.
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