Date of Degree

2012

Document Type

PhD diss.

Degree Name

PhD (Doctor of Philosophy)

Department

Chemistry

First Advisor

Johna Leddy

Abstract

This research exploits mild sonication in a thin layer electrochemical cell to enhance rates of reaction in systems under voltammetric perturbation. Sound waves propagate through a thin layer of condensed fluid to provide energy to the electrode solution interface in the form of pressure and temperature. The sonic energy provided in three dimensions can be exploited to enhance rates of heterogeneous electron transfer as the energy is harnessed at the two dimensional electrode interface. Enhanced rates of heterogeneous electron transfer are of interest both for fundamental reasons and for exploitation in electrochemical energy systems.

The initial pilot studies were directed at demonstrating the impact of acoustic energy on heterogenous electron transfer. Redox couples with different electron transfer rates were evaluated. Whereas compounds with reversible electron transfer kinetics demonstrated little improvement, redox couples such as ferric ion (Fe3+) with slow electron transfer kinetics exhibited an increase in the standard heterogeneous electron transfer rate constant, k0 with an increase in acoustic energy.

The reduction of oxygen is a complex four proton, four electron process that is of technological importance. Slow kinetics of the oxygen reduction is a primary loss of efficiency in electrochemical power sources. Much like the ferric ion, oxygen kinetic rats improve. Preliminary studies in the oxidation of methanol demonstrated a sonocatalyic effect in methanol electrolysis that is of particular interest for the development of liquid based fuel cells.

Sonication can both clean and destroy surface materials. The cleaning power inherent in sonication improves electrocatalysis and removes deposits and oxides from the electrode surface.

Pages

xv, 161

Bibliography

158-161

Copyright

Copyright 2012 Chester Duda

Included in

Chemistry Commons

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