Tuning the reactivity of carbon surfaces with oxygen-containing functional groups
Abstract Oxygen-containing carbons are promising supports and metal-free catalysts for many reactions. However, distinguishing the role of various oxygen functional groups and quantifying and tuning each functionality is still difficult. Here we investigate the role of Brønsted acidic oxygen-contain...
| Main Authors: | , , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2023-04-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-37962-3 |
| _version_ | 1827961173698412544 |
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| author | Jiahua Zhou Piaoping Yang Pavel A. Kots Maximilian Cohen Ying Chen Caitlin M. Quinn Matheus Dorneles de Mello J. Anibal Boscoboinik Wendy J. Shaw Stavros Caratzoulas Weiqing Zheng Dionisios G. Vlachos |
| author_facet | Jiahua Zhou Piaoping Yang Pavel A. Kots Maximilian Cohen Ying Chen Caitlin M. Quinn Matheus Dorneles de Mello J. Anibal Boscoboinik Wendy J. Shaw Stavros Caratzoulas Weiqing Zheng Dionisios G. Vlachos |
| author_sort | Jiahua Zhou |
| collection | DOAJ |
| description | Abstract Oxygen-containing carbons are promising supports and metal-free catalysts for many reactions. However, distinguishing the role of various oxygen functional groups and quantifying and tuning each functionality is still difficult. Here we investigate the role of Brønsted acidic oxygen-containing functional groups by synthesizing a diverse library of materials. By combining acid-catalyzed elimination probe chemistry, comprehensive surface characterizations, 15N isotopically labeled acetonitrile adsorption coupled with magic-angle spinning nuclear magnetic resonance, machine learning, and density-functional theory calculations, we demonstrate that phenolic is the main acid site in gas-phase chemistries and unexpectedly carboxylic groups are much less acidic than phenolic groups in the graphitized mesoporous carbon due to electron density delocalization induced by the aromatic rings of graphitic carbon. The methodology can identify acidic sites in oxygenated carbon materials in solid acid catalyst-driven chemistry. |
| first_indexed | 2024-04-09T16:22:47Z |
| format | Article |
| id | doaj.art-5bbe7d4bc1b34016a02ca8adfe5a3b78 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-04-09T16:22:47Z |
| publishDate | 2023-04-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-5bbe7d4bc1b34016a02ca8adfe5a3b782023-04-23T11:23:07ZengNature PortfolioNature Communications2041-17232023-04-0114111110.1038/s41467-023-37962-3Tuning the reactivity of carbon surfaces with oxygen-containing functional groupsJiahua Zhou0Piaoping Yang1Pavel A. Kots2Maximilian Cohen3Ying Chen4Caitlin M. Quinn5Matheus Dorneles de Mello6J. Anibal Boscoboinik7Wendy J. Shaw8Stavros Caratzoulas9Weiqing Zheng10Dionisios G. Vlachos11Department of Chemical and Biomolecular Engineering, University of DelawareDepartment of Chemical and Biomolecular Engineering, University of DelawareDepartment of Chemical and Biomolecular Engineering, University of DelawareDepartment of Chemical and Biomolecular Engineering, University of DelawarePacific Northwest National LaboratoryDepartment of Chemistry and Biochemistry, University of DelawareCatalysis Center for Energy Innovation, University of DelawareCatalysis Center for Energy Innovation, University of DelawarePacific Northwest National LaboratoryCatalysis Center for Energy Innovation, University of DelawareCatalysis Center for Energy Innovation, University of DelawareDepartment of Chemical and Biomolecular Engineering, University of DelawareAbstract Oxygen-containing carbons are promising supports and metal-free catalysts for many reactions. However, distinguishing the role of various oxygen functional groups and quantifying and tuning each functionality is still difficult. Here we investigate the role of Brønsted acidic oxygen-containing functional groups by synthesizing a diverse library of materials. By combining acid-catalyzed elimination probe chemistry, comprehensive surface characterizations, 15N isotopically labeled acetonitrile adsorption coupled with magic-angle spinning nuclear magnetic resonance, machine learning, and density-functional theory calculations, we demonstrate that phenolic is the main acid site in gas-phase chemistries and unexpectedly carboxylic groups are much less acidic than phenolic groups in the graphitized mesoporous carbon due to electron density delocalization induced by the aromatic rings of graphitic carbon. The methodology can identify acidic sites in oxygenated carbon materials in solid acid catalyst-driven chemistry.https://doi.org/10.1038/s41467-023-37962-3 |
| spellingShingle | Jiahua Zhou Piaoping Yang Pavel A. Kots Maximilian Cohen Ying Chen Caitlin M. Quinn Matheus Dorneles de Mello J. Anibal Boscoboinik Wendy J. Shaw Stavros Caratzoulas Weiqing Zheng Dionisios G. Vlachos Tuning the reactivity of carbon surfaces with oxygen-containing functional groups Nature Communications |
| title | Tuning the reactivity of carbon surfaces with oxygen-containing functional groups |
| title_full | Tuning the reactivity of carbon surfaces with oxygen-containing functional groups |
| title_fullStr | Tuning the reactivity of carbon surfaces with oxygen-containing functional groups |
| title_full_unstemmed | Tuning the reactivity of carbon surfaces with oxygen-containing functional groups |
| title_short | Tuning the reactivity of carbon surfaces with oxygen-containing functional groups |
| title_sort | tuning the reactivity of carbon surfaces with oxygen containing functional groups |
| url | https://doi.org/10.1038/s41467-023-37962-3 |
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