Surface-bound molecular rulers for probing the electrical double layer
Herein, we report the first experimental investigation on the effect of varying the position of redox-active moieties, within the electrical double layer, on the apparent formal potential and on the electron transfer rate constant. This was achieved using a rigid class of molecules, norbornylogous b...
| Main Authors: | , , , |
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| Format: | Journal Article |
| Published: |
American Chemical Society
2012
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| Online Access: | http://hdl.handle.net/20.500.11937/16913 |
| _version_ | 1848749312772669440 |
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| author | Eggers, P. Darwish, Nadim Paddon-Row, M. Gooding, J. |
| author_facet | Eggers, P. Darwish, Nadim Paddon-Row, M. Gooding, J. |
| author_sort | Eggers, P. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | Herein, we report the first experimental investigation on the effect of varying the position of redox-active moieties, within the electrical double layer, on the apparent formal potential and on the electron transfer rate constant. This was achieved using a rigid class of molecules, norbornylogous bridges, to place redox species (ferrocene) at a fixed position above the surface of the electrode. Cyclic voltammetry and alternating current voltammetry were used to calculate the apparent formal potential and the electron transfer rate constant for the electron transfer between the ferrocene and the gold electrode. We use the effect of electric field on the apparent formal potential measurement of the surface-bound redox species to calculate the potential drop from the initiation of the electrical double layer to different distances above it. It was found that self-assembled monolayers formed from ?- hydroxyalkanethiol have a potential profile very similar to that described by classical theories for bare metal electrodes. A steep drop in potential in the Stern layer was observed followed by a smaller potential drop in the Gouy-Chapman layer. The electron transfer rate constant was found to decrease as the distance between the ferrocene moiety and the initiation of the double layer is increased. Thus, the electron transfer rate constant appears to be dependent on ion concentration. |
| first_indexed | 2025-11-14T07:18:57Z |
| format | Journal Article |
| id | curtin-20.500.11937-16913 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T07:18:57Z |
| publishDate | 2012 |
| publisher | American Chemical Society |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-169132017-09-13T15:43:55Z Surface-bound molecular rulers for probing the electrical double layer Eggers, P. Darwish, Nadim Paddon-Row, M. Gooding, J. Herein, we report the first experimental investigation on the effect of varying the position of redox-active moieties, within the electrical double layer, on the apparent formal potential and on the electron transfer rate constant. This was achieved using a rigid class of molecules, norbornylogous bridges, to place redox species (ferrocene) at a fixed position above the surface of the electrode. Cyclic voltammetry and alternating current voltammetry were used to calculate the apparent formal potential and the electron transfer rate constant for the electron transfer between the ferrocene and the gold electrode. We use the effect of electric field on the apparent formal potential measurement of the surface-bound redox species to calculate the potential drop from the initiation of the electrical double layer to different distances above it. It was found that self-assembled monolayers formed from ?- hydroxyalkanethiol have a potential profile very similar to that described by classical theories for bare metal electrodes. A steep drop in potential in the Stern layer was observed followed by a smaller potential drop in the Gouy-Chapman layer. The electron transfer rate constant was found to decrease as the distance between the ferrocene moiety and the initiation of the double layer is increased. Thus, the electron transfer rate constant appears to be dependent on ion concentration. 2012 Journal Article http://hdl.handle.net/20.500.11937/16913 10.1021/ja301509h American Chemical Society restricted |
| spellingShingle | Eggers, P. Darwish, Nadim Paddon-Row, M. Gooding, J. Surface-bound molecular rulers for probing the electrical double layer |
| title | Surface-bound molecular rulers for probing the electrical double layer |
| title_full | Surface-bound molecular rulers for probing the electrical double layer |
| title_fullStr | Surface-bound molecular rulers for probing the electrical double layer |
| title_full_unstemmed | Surface-bound molecular rulers for probing the electrical double layer |
| title_short | Surface-bound molecular rulers for probing the electrical double layer |
| title_sort | surface-bound molecular rulers for probing the electrical double layer |
| url | http://hdl.handle.net/20.500.11937/16913 |