Electrocatalytic dioxygen reduction by surface-immobilized molecular copper complexes
Abstract/Contents
- Abstract
- Surface-immobilized Cu(I) complexes with substituted 1,10-phenantrholines and related ligands are competent electrocatalysts for the 4-electron reduction of dioxygen to water. A large library of Cu(I) complexes has been adsorbed to the carbon electrodes by either physisorption or by covalent attachment directly to the carbon surface. The rate of electrocatalytic dioxygen reduction is studied using the hydrodynamic techniques rotating-disk voltammetry and rotating-ring disk voltammetry. From these studies, potential-dependent kinetic rates are established. The onset potential and kinetic rate for O2 reduction can be modulated by changing the nature of the ligand in the immobilized Cu complex, or by changing the nature by which the Cu complex is attached to the surface. Evidence is presented that the 4-electron reduction of dioxygen to water operates by a binuclear pathway that requires 2 Cu catalysts in close proximity to coordinate and reduce a single dioxygen molecule. Mechanisms are proposed for dioxygen reduction by adsorbed Cu(I) complexes that are consistent with the observed data. Electrocatalytic hydrogen peroxide reduction has also been studied briefly in an attempt to intercept the dioxygen-reduction mechanism, and the results of these studies are reported.
Description
| Type of resource | text |
|---|---|
| Form | electronic; electronic resource; remote |
| Extent | 1 online resource. |
| Publication date | 2010 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Associated with | McCrory, Charles Chauncey Luther |
|---|---|
| Associated with | Stanford University, Department of Chemistry |
| Primary advisor | Chidsey, Christopher E. D. (Christopher Elisha Dunn) |
| Thesis advisor | Chidsey, Christopher E. D. (Christopher Elisha Dunn) |
| Thesis advisor | Pecora, Robert, 1938- |
| Thesis advisor | Stack, T. (T. Daniel P.), 1959- |
| Advisor | Pecora, Robert, 1938- |
| Advisor | Stack, T. (T. Daniel P.), 1959- |
Subjects
| Genre | Theses |
|---|
Bibliographic information
| Statement of responsibility | Charles Chauncey Luther McCrory. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Ph.D. Stanford University 2010 |
| Location | electronic resource |
Access conditions
- Copyright
- © 2010 by Charles Chauncey Luther McCrory
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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