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


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.


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:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11285
Deposited By: Lisa Fischelis
Deposited On:27 Nov 2018 21:15
Last Modified:02 Dec 2020 01:30

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