Chlorination and oxygenation of carbon electrodes for covalent attachment of thiol-terminated molecules
This study reports covalent edge plane chlorination of carbon electrodes and their subsequent functionalization with thiol-containing redox-active molecules. Specifically, the reactivity of edge C-H groups on glassy carbon (GC) and carbon powder (CP) electrodes with chlorinating reagents, iodine mon...
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| Format: | Article |
| Language: | English |
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Elsevier
2025-08-01
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| Series: | Carbon Trends |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2667056925000896 |
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| author | Xin Zheng Igor L. Bolotin Beria Tanriover Kumuditha Rathnayake Erik J. Askins Jordi Cabana Neal P. Mankad Ksenija D. Glusac |
| author_facet | Xin Zheng Igor L. Bolotin Beria Tanriover Kumuditha Rathnayake Erik J. Askins Jordi Cabana Neal P. Mankad Ksenija D. Glusac |
| author_sort | Xin Zheng |
| collection | DOAJ |
| description | This study reports covalent edge plane chlorination of carbon electrodes and their subsequent functionalization with thiol-containing redox-active molecules. Specifically, the reactivity of edge C-H groups on glassy carbon (GC) and carbon powder (CP) electrodes with chlorinating reagents, iodine monochloride and iron(III) chloride, was investigated under varying reaction conditions. The degree of chlorination was evaluated using X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (NMR) spectroscopy and vibrational spectroscopy. Chlorination was observed under all tested conditions, with the C-H to C-Cl conversion strongly influenced by electrode pretreatment, reaction time, and type of carbon electrode used. We further investigated the reactivity of surface C-Cl groups in nucleophilic aromatic substitution reactions with (6-mercaptohexyl)ferrocene, (Fc(CH2)6SH). The electrochemical properties of the modified electrodes were compared with those of control samples prepared using anodized carbon and gold electrodes. XPS, infrared spectroscopy, and cyclic voltammetry confirmed the successful thiol-ferrocene functionalization of the chlorinated electrodes, though higher surface coverages were achieved on anodized carbon electrodes. These results indicate that thiols react not only with C-Cl groups but also with oxygen-containing groups present on anodized carbon surfaces. We further explored this reactivity in the use of benzene-1,2,4,5-tetrathiol as a bridging linker to anchor a molybdenum-based complex onto chlorinated and anodized carbon surface. |
| format | Article |
| id | doaj-art-07a9666806ba4ec38b3dc8a43b9c70b0 |
| institution | OA Journals |
| issn | 2667-0569 |
| language | English |
| publishDate | 2025-08-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Carbon Trends |
| spelling | doaj-art-07a9666806ba4ec38b3dc8a43b9c70b02025-08-20T02:20:41ZengElsevierCarbon Trends2667-05692025-08-012010053910.1016/j.cartre.2025.100539Chlorination and oxygenation of carbon electrodes for covalent attachment of thiol-terminated moleculesXin Zheng0Igor L. Bolotin1Beria Tanriover2Kumuditha Rathnayake3Erik J. Askins4Jordi Cabana5Neal P. Mankad6Ksenija D. Glusac7Department of Chemistry, University of Illinois Chicago, Chicago, IL 60607, USADepartment of Chemistry, University of Illinois Chicago, Chicago, IL 60607, USADepartment of Chemistry, University of Illinois Chicago, Chicago, IL 60607, USADepartment of Chemistry, University of Illinois Chicago, Chicago, IL 60607, USADepartment of Chemistry, University of Illinois Chicago, Chicago, IL 60607, USADepartment of Chemistry, University of Illinois Chicago, Chicago, IL 60607, USA; Materials Science Division, Argonne National Laboratory, Lemont, IL 60439, USADepartment of Chemistry, University of Illinois Chicago, Chicago, IL 60607, USADepartment of Chemistry, University of Illinois Chicago, Chicago, IL 60607, USA; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439, USA; Corresponding author at: Department of Chemistry, University of Illinois Chicago, Chicago, IL 60607, USA.This study reports covalent edge plane chlorination of carbon electrodes and their subsequent functionalization with thiol-containing redox-active molecules. Specifically, the reactivity of edge C-H groups on glassy carbon (GC) and carbon powder (CP) electrodes with chlorinating reagents, iodine monochloride and iron(III) chloride, was investigated under varying reaction conditions. The degree of chlorination was evaluated using X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (NMR) spectroscopy and vibrational spectroscopy. Chlorination was observed under all tested conditions, with the C-H to C-Cl conversion strongly influenced by electrode pretreatment, reaction time, and type of carbon electrode used. We further investigated the reactivity of surface C-Cl groups in nucleophilic aromatic substitution reactions with (6-mercaptohexyl)ferrocene, (Fc(CH2)6SH). The electrochemical properties of the modified electrodes were compared with those of control samples prepared using anodized carbon and gold electrodes. XPS, infrared spectroscopy, and cyclic voltammetry confirmed the successful thiol-ferrocene functionalization of the chlorinated electrodes, though higher surface coverages were achieved on anodized carbon electrodes. These results indicate that thiols react not only with C-Cl groups but also with oxygen-containing groups present on anodized carbon surfaces. We further explored this reactivity in the use of benzene-1,2,4,5-tetrathiol as a bridging linker to anchor a molybdenum-based complex onto chlorinated and anodized carbon surface.http://www.sciencedirect.com/science/article/pii/S2667056925000896Carbon electrode modificationsGlassy carbonCarbon black powderChlorinationAlkanethiolsAromatic thiols |
| spellingShingle | Xin Zheng Igor L. Bolotin Beria Tanriover Kumuditha Rathnayake Erik J. Askins Jordi Cabana Neal P. Mankad Ksenija D. Glusac Chlorination and oxygenation of carbon electrodes for covalent attachment of thiol-terminated molecules Carbon Trends Carbon electrode modifications Glassy carbon Carbon black powder Chlorination Alkanethiols Aromatic thiols |
| title | Chlorination and oxygenation of carbon electrodes for covalent attachment of thiol-terminated molecules |
| title_full | Chlorination and oxygenation of carbon electrodes for covalent attachment of thiol-terminated molecules |
| title_fullStr | Chlorination and oxygenation of carbon electrodes for covalent attachment of thiol-terminated molecules |
| title_full_unstemmed | Chlorination and oxygenation of carbon electrodes for covalent attachment of thiol-terminated molecules |
| title_short | Chlorination and oxygenation of carbon electrodes for covalent attachment of thiol-terminated molecules |
| title_sort | chlorination and oxygenation of carbon electrodes for covalent attachment of thiol terminated molecules |
| topic | Carbon electrode modifications Glassy carbon Carbon black powder Chlorination Alkanethiols Aromatic thiols |
| url | http://www.sciencedirect.com/science/article/pii/S2667056925000896 |
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