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Adsorption and Electrochemistry of BIS-1, 10-Phenanthroline Complexes of Copper (I,II) and Fungal Laccase A

Citation

Lee, Chi-Woo (1984) Adsorption and Electrochemistry of BIS-1, 10-Phenanthroline Complexes of Copper (I,II) and Fungal Laccase A. Dissertation (Ph.D.), California Institute of Technology. https://resolver.caltech.edu/CaltechTHESIS:11272018-091510836

Abstract

This thesis is an outcome of the efforts directed toward the theme "Electrocatalysis of dioxygen reduction by copper- containing molecules adsorbed on graphite electrodes."

In the first part, an electrochemical measurement of the rate of electron exchange between Cu(phen)2+ adsorbed on graphite and Cu(phen)2++ in solution is described. The rate constant was estimated to be ca. 105 M-1 s-1 by using rotating disk voltammetry. The origin of the previously reported but widely discrepant values (5 x 107 M-1 s-1 and 50 M-1 s-1) in the literature is discussed, and a new estimate of ca. 104 M-1 s-1 is obtained by applying Marcus theory in a form that allows explicitly for differences in reorganization energy between the oxidized and reduced halves of the reacting redox couples. The electrocatalytic studies of dioxygen reduction by Cu(phen)2+ could not be done due to the low signal-to-noise ratio.

In the second part, the bioelectrocatalytic reduction of molecular oxygen by reduced fungal laccase A immobilized on pyrolytic graphite is described. The reduction produces exclusively water in the potential range studied (< 0 V vs. SSCE). The catalytic activity reaches its maximum at pH 3~4, and the lower limit on rate constant for the reduction in this pH range was estimated to be 1.5 x 104 M-1 s-1.

Three appendices describe (i) potential step hydrodynamic chronocoulometry, (ii) a new method to determine the self- exchange rate constant for the redox couple in which the coordination numbers depend on the oxidation states, and (iii) a novel electrochemical method of detecting H2O2.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Bercaw, John E.
Thesis Committee:
  • Anson, Fred C. (chair)
  • Gray, Harry B.
  • Marcus, Rudolph A.
  • Bercaw, John E.
Defense Date:10 October 1983
Record Number:CaltechTHESIS:11272018-091510836
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:11272018-091510836
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11285
Collection:CaltechTHESIS
Deposited By: Lisa Fischelis
Deposited On:27 Nov 2018 21:15
Last Modified:02 Dec 2020 01:30

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