Comparative Proton Coupled Electron Transfer at Glassy Carbon and Boron‐Doped Diamond Electrodes
Abstract The surface modification of carbon electrodes is an area of great interest in both fundamental and applied electrochemistry. Herein we demonstrate a reliable route for the modification of sp3 boron‐doped diamond electrodes through a diazonium reduction and subsequent solid phase synthesis t...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2024-02-01
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| Series: | ChemElectroChem |
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| Online Access: | https://doi.org/10.1002/celc.202300470 |
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| author | Shane P. O. Neill Dr. Adrià Martínez‐Aviñó Charlie Keene Sammi Hassan Catriona Houston Shekemi Denuga Emer B. Farrell Dr. Guzmán Gil‐Ramírez Dr. Robert P. Johnson |
| author_facet | Shane P. O. Neill Dr. Adrià Martínez‐Aviñó Charlie Keene Sammi Hassan Catriona Houston Shekemi Denuga Emer B. Farrell Dr. Guzmán Gil‐Ramírez Dr. Robert P. Johnson |
| author_sort | Shane P. O. Neill |
| collection | DOAJ |
| description | Abstract The surface modification of carbon electrodes is an area of great interest in both fundamental and applied electrochemistry. Herein we demonstrate a reliable route for the modification of sp3 boron‐doped diamond electrodes through a diazonium reduction and subsequent solid phase synthesis to produce a stable, immobilised layer of surface‐bound anthraquinone. The electron transfer kinetics, surface coverage, and pKa of the immobilised anthraquinone were investigated and compared to those of anthraquinone immobilised via an identical synthetic route onto a glassy carbon sp2 interface. The pKa of anthraquinone was found to be 9.1 on glassy carbon but 6.6 on boron‐doped diamond. Differences in pKa were observed despite the use of identical surface modification strategies and the achievement of comparable surface densities for both types of electrode, and are attributed to the differing dielectric properties of the surface‐modified layers atop either an sp2 or sp3 interface. These results highlight how the underlying substrate can greatly influence the fundamental chemical and electrochemical properties of immobilised molecules, as well as the need for caution when applying well‐established sp2 solid phase synthesis methodologies to sp3 substrates. |
| first_indexed | 2024-03-08T00:19:58Z |
| format | Article |
| id | doaj.art-bf8fbb42c90b42faad00e087cff93187 |
| institution | Directory Open Access Journal |
| issn | 2196-0216 |
| language | English |
| last_indexed | 2024-04-24T07:41:41Z |
| publishDate | 2024-02-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemElectroChem |
| spelling | doaj.art-bf8fbb42c90b42faad00e087cff931872024-04-19T13:10:31ZengWiley-VCHChemElectroChem2196-02162024-02-01114n/an/a10.1002/celc.202300470Comparative Proton Coupled Electron Transfer at Glassy Carbon and Boron‐Doped Diamond ElectrodesShane P. O. Neill0Dr. Adrià Martínez‐Aviñó1Charlie Keene2Sammi Hassan3Catriona Houston4Shekemi Denuga5Emer B. Farrell6Dr. Guzmán Gil‐Ramírez7Dr. Robert P. Johnson8School of Chemistry University College Dublin Belfield Dublin 4 IrelandSchool of Chemistry University College Dublin Belfield Dublin 4 IrelandSchool of Chemistry University of Lincoln Lincoln LN6 7DL UKSchool of Chemistry University of Lincoln Lincoln LN6 7DL UKSchool of Chemistry University College Dublin Belfield Dublin 4 IrelandSchool of Chemistry University College Dublin Belfield Dublin 4 IrelandSchool of Chemistry University College Dublin Belfield Dublin 4 IrelandSchool of Chemistry University of Lincoln Lincoln LN6 7DL UKSchool of Chemistry University College Dublin Belfield Dublin 4 IrelandAbstract The surface modification of carbon electrodes is an area of great interest in both fundamental and applied electrochemistry. Herein we demonstrate a reliable route for the modification of sp3 boron‐doped diamond electrodes through a diazonium reduction and subsequent solid phase synthesis to produce a stable, immobilised layer of surface‐bound anthraquinone. The electron transfer kinetics, surface coverage, and pKa of the immobilised anthraquinone were investigated and compared to those of anthraquinone immobilised via an identical synthetic route onto a glassy carbon sp2 interface. The pKa of anthraquinone was found to be 9.1 on glassy carbon but 6.6 on boron‐doped diamond. Differences in pKa were observed despite the use of identical surface modification strategies and the achievement of comparable surface densities for both types of electrode, and are attributed to the differing dielectric properties of the surface‐modified layers atop either an sp2 or sp3 interface. These results highlight how the underlying substrate can greatly influence the fundamental chemical and electrochemical properties of immobilised molecules, as well as the need for caution when applying well‐established sp2 solid phase synthesis methodologies to sp3 substrates.https://doi.org/10.1002/celc.202300470AnthraquinoneBoron-Doped DiamondGlassy CarbonpKa |
| spellingShingle | Shane P. O. Neill Dr. Adrià Martínez‐Aviñó Charlie Keene Sammi Hassan Catriona Houston Shekemi Denuga Emer B. Farrell Dr. Guzmán Gil‐Ramírez Dr. Robert P. Johnson Comparative Proton Coupled Electron Transfer at Glassy Carbon and Boron‐Doped Diamond Electrodes ChemElectroChem Anthraquinone Boron-Doped Diamond Glassy Carbon pKa |
| title | Comparative Proton Coupled Electron Transfer at Glassy Carbon and Boron‐Doped Diamond Electrodes |
| title_full | Comparative Proton Coupled Electron Transfer at Glassy Carbon and Boron‐Doped Diamond Electrodes |
| title_fullStr | Comparative Proton Coupled Electron Transfer at Glassy Carbon and Boron‐Doped Diamond Electrodes |
| title_full_unstemmed | Comparative Proton Coupled Electron Transfer at Glassy Carbon and Boron‐Doped Diamond Electrodes |
| title_short | Comparative Proton Coupled Electron Transfer at Glassy Carbon and Boron‐Doped Diamond Electrodes |
| title_sort | comparative proton coupled electron transfer at glassy carbon and boron doped diamond electrodes |
| topic | Anthraquinone Boron-Doped Diamond Glassy Carbon pKa |
| url | https://doi.org/10.1002/celc.202300470 |
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