Boron-doped diamond electrodes in organic media: Electrochemical activation and selectivity effects
This study highlights the effects of the electrochemical surface pre-treatment of polished polycrystalline boron-doped diamond electrodes in ethanol on electron transfer to organic redox systems. A novel "activation" procedure based on cathodic polarisation in ethanol (0.01 M NBu4PF6) is p...
| Main Authors: | , , , , , |
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| Format: | Journal article |
| Language: | English |
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2007
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| _version_ | 1826289365109702656 |
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| author | Kulandainathan, M Hall, C Wolverson, D Foord, J MacDonald, S Marken, F |
| author_facet | Kulandainathan, M Hall, C Wolverson, D Foord, J MacDonald, S Marken, F |
| author_sort | Kulandainathan, M |
| collection | OXFORD |
| description | This study highlights the effects of the electrochemical surface pre-treatment of polished polycrystalline boron-doped diamond electrodes in ethanol on electron transfer to organic redox systems. A novel "activation" procedure based on cathodic polarisation in ethanol (0.01 M NBu4PF6) is proposed and shown to be highly effective in promoting electron transfer to the aqueous Fe (CN)63 - / 4 - redox system. For redox systems in acetonitrile, effects on electron transfer processes are strongly dependent on the type of electron transfer process. For decamethylferrocene+/0, decamethylcobaltocene+/0, methyviologen2+/+, and for methylviologen+/0 redox systems essentially reversible electron transfer is observed irrespective of the pre-treatment of the boron-doped diamond electrode. For the benzoquinone0/- redox system insignificant changes occur but for the benzoquinone-/2- process a more dramatic change in electron transfer kinetics is observed (after cathodic polarisation in ethanol) consistent with an improved interfacial electron transfer (a 4.6 × increase in peak current occurs). Finally, the tetraethyl-ethylenetetracarboxylate0/- system is investigated as a model olefin redox system. Again changes in reactivity occur (a 4.0 × increase in peak current) at the cathodically pre-treated boron-doped diamond electrode. XPS surface analysis data reveal only insignificant changes in the chemical composition of the boron-doped diamond surface before and after activation and therefore a predominantly electronic mechanism for the "activation" process is proposed. In future selectivity effects for electron transfer at boron-doped diamond electrode surfaces could be introduced intentionally and used beneficially for chemo-selective electro-organic processes. © 2007 Elsevier B.V. All rights reserved. |
| first_indexed | 2024-03-07T02:27:46Z |
| format | Journal article |
| id | oxford-uuid:a636591c-74b7-46ad-ac2c-59eeaaa4beb6 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T02:27:46Z |
| publishDate | 2007 |
| record_format | dspace |
| spelling | oxford-uuid:a636591c-74b7-46ad-ac2c-59eeaaa4beb62022-03-27T02:45:36ZBoron-doped diamond electrodes in organic media: Electrochemical activation and selectivity effectsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:a636591c-74b7-46ad-ac2c-59eeaaa4beb6EnglishSymplectic Elements at Oxford2007Kulandainathan, MHall, CWolverson, DFoord, JMacDonald, SMarken, FThis study highlights the effects of the electrochemical surface pre-treatment of polished polycrystalline boron-doped diamond electrodes in ethanol on electron transfer to organic redox systems. A novel "activation" procedure based on cathodic polarisation in ethanol (0.01 M NBu4PF6) is proposed and shown to be highly effective in promoting electron transfer to the aqueous Fe (CN)63 - / 4 - redox system. For redox systems in acetonitrile, effects on electron transfer processes are strongly dependent on the type of electron transfer process. For decamethylferrocene+/0, decamethylcobaltocene+/0, methyviologen2+/+, and for methylviologen+/0 redox systems essentially reversible electron transfer is observed irrespective of the pre-treatment of the boron-doped diamond electrode. For the benzoquinone0/- redox system insignificant changes occur but for the benzoquinone-/2- process a more dramatic change in electron transfer kinetics is observed (after cathodic polarisation in ethanol) consistent with an improved interfacial electron transfer (a 4.6 × increase in peak current occurs). Finally, the tetraethyl-ethylenetetracarboxylate0/- system is investigated as a model olefin redox system. Again changes in reactivity occur (a 4.0 × increase in peak current) at the cathodically pre-treated boron-doped diamond electrode. XPS surface analysis data reveal only insignificant changes in the chemical composition of the boron-doped diamond surface before and after activation and therefore a predominantly electronic mechanism for the "activation" process is proposed. In future selectivity effects for electron transfer at boron-doped diamond electrode surfaces could be introduced intentionally and used beneficially for chemo-selective electro-organic processes. © 2007 Elsevier B.V. All rights reserved. |
| spellingShingle | Kulandainathan, M Hall, C Wolverson, D Foord, J MacDonald, S Marken, F Boron-doped diamond electrodes in organic media: Electrochemical activation and selectivity effects |
| title | Boron-doped diamond electrodes in organic media: Electrochemical activation and selectivity effects |
| title_full | Boron-doped diamond electrodes in organic media: Electrochemical activation and selectivity effects |
| title_fullStr | Boron-doped diamond electrodes in organic media: Electrochemical activation and selectivity effects |
| title_full_unstemmed | Boron-doped diamond electrodes in organic media: Electrochemical activation and selectivity effects |
| title_short | Boron-doped diamond electrodes in organic media: Electrochemical activation and selectivity effects |
| title_sort | boron doped diamond electrodes in organic media electrochemical activation and selectivity effects |
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