Combining synchrotron vacuum-ultraviolet photoionization mass spectrometry and gas chromatography–mass spectrometry for isomer-specific mechanistic analysis with application to the benzyl self-reaction
Abstract Elucidating the formation mechanism of polycyclic aromatic hydrocarbons (PAHs) is crucial to understand processes in the contexts of combustion, environmental science, astrochemistry, and nanomaterials synthesis. An excited electronic-state pathway has been proposed to account for the forma...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-12-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-53889-9 |
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| author | Guangxian Xu Hong Wang Jinyang Zhang Jiao Gao Jiwen Guan Qiang Xu Donald G. Truhlar Zhandong Wang |
| author_facet | Guangxian Xu Hong Wang Jinyang Zhang Jiao Gao Jiwen Guan Qiang Xu Donald G. Truhlar Zhandong Wang |
| author_sort | Guangxian Xu |
| collection | DOAJ |
| description | Abstract Elucidating the formation mechanism of polycyclic aromatic hydrocarbons (PAHs) is crucial to understand processes in the contexts of combustion, environmental science, astrochemistry, and nanomaterials synthesis. An excited electronic-state pathway has been proposed to account for the formation of 14π aromatic anthracene in the benzyl (b-C7H7) self-reaction. Here, to improve our understanding of anthracene formation, we investigate C7H7 bimolecular reactions in a tubular SiC microreactor through an isomer-resolved method that combines in situ synchrotron-radiation VUV photoionization mass spectrometry and ex-situ gas chromatography–mass spectrometry. We observe the formation of o-tolyl (o-C7H7) radical isomer, and identify several C14H10 products (diphenylacetylene, phenanthrene and anthracene) and key C14H14 and C14H12 intermediates. These isomer-specific results support the occurrence of reactions on the electronic ground-state potential energy surface, with no evidence for key intermediates of the proposed excited-state pathway as the key pathway. Furthermore, theoretical calculations unveil new facile reaction pathways that may contribute to the enhanced production of anthracene, and these mechanistic findings are further substantiated by pyrolysis experiments. The results add insight into the molecular formation of PAHs in C7H7 bimolecular reaction, and contribute to establishing accurate models to predict PAH chemistry in diverse laboratory, environmental, and extraterrestrial contexts. |
| format | Article |
| id | doaj-art-122ad79991344a5e93e7b68faffa96a2 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-122ad79991344a5e93e7b68faffa96a22025-01-05T12:36:14ZengNature PortfolioNature Communications2041-17232024-12-0115111010.1038/s41467-024-53889-9Combining synchrotron vacuum-ultraviolet photoionization mass spectrometry and gas chromatography–mass spectrometry for isomer-specific mechanistic analysis with application to the benzyl self-reactionGuangxian Xu0Hong Wang1Jinyang Zhang2Jiao Gao3Jiwen Guan4Qiang Xu5Donald G. Truhlar6Zhandong Wang7National Synchrotron Radiation Laboratory, University of Science and Technology of ChinaNational Synchrotron Radiation Laboratory, University of Science and Technology of ChinaNational Synchrotron Radiation Laboratory, University of Science and Technology of ChinaSchool of Pharmacy, Anhui Medical CollegeNational Synchrotron Radiation Laboratory, University of Science and Technology of ChinaNational Synchrotron Radiation Laboratory, University of Science and Technology of ChinaDepartment of Chemistry, University of MinnesotaNational Synchrotron Radiation Laboratory, University of Science and Technology of ChinaAbstract Elucidating the formation mechanism of polycyclic aromatic hydrocarbons (PAHs) is crucial to understand processes in the contexts of combustion, environmental science, astrochemistry, and nanomaterials synthesis. An excited electronic-state pathway has been proposed to account for the formation of 14π aromatic anthracene in the benzyl (b-C7H7) self-reaction. Here, to improve our understanding of anthracene formation, we investigate C7H7 bimolecular reactions in a tubular SiC microreactor through an isomer-resolved method that combines in situ synchrotron-radiation VUV photoionization mass spectrometry and ex-situ gas chromatography–mass spectrometry. We observe the formation of o-tolyl (o-C7H7) radical isomer, and identify several C14H10 products (diphenylacetylene, phenanthrene and anthracene) and key C14H14 and C14H12 intermediates. These isomer-specific results support the occurrence of reactions on the electronic ground-state potential energy surface, with no evidence for key intermediates of the proposed excited-state pathway as the key pathway. Furthermore, theoretical calculations unveil new facile reaction pathways that may contribute to the enhanced production of anthracene, and these mechanistic findings are further substantiated by pyrolysis experiments. The results add insight into the molecular formation of PAHs in C7H7 bimolecular reaction, and contribute to establishing accurate models to predict PAH chemistry in diverse laboratory, environmental, and extraterrestrial contexts.https://doi.org/10.1038/s41467-024-53889-9 |
| spellingShingle | Guangxian Xu Hong Wang Jinyang Zhang Jiao Gao Jiwen Guan Qiang Xu Donald G. Truhlar Zhandong Wang Combining synchrotron vacuum-ultraviolet photoionization mass spectrometry and gas chromatography–mass spectrometry for isomer-specific mechanistic analysis with application to the benzyl self-reaction Nature Communications |
| title | Combining synchrotron vacuum-ultraviolet photoionization mass spectrometry and gas chromatography–mass spectrometry for isomer-specific mechanistic analysis with application to the benzyl self-reaction |
| title_full | Combining synchrotron vacuum-ultraviolet photoionization mass spectrometry and gas chromatography–mass spectrometry for isomer-specific mechanistic analysis with application to the benzyl self-reaction |
| title_fullStr | Combining synchrotron vacuum-ultraviolet photoionization mass spectrometry and gas chromatography–mass spectrometry for isomer-specific mechanistic analysis with application to the benzyl self-reaction |
| title_full_unstemmed | Combining synchrotron vacuum-ultraviolet photoionization mass spectrometry and gas chromatography–mass spectrometry for isomer-specific mechanistic analysis with application to the benzyl self-reaction |
| title_short | Combining synchrotron vacuum-ultraviolet photoionization mass spectrometry and gas chromatography–mass spectrometry for isomer-specific mechanistic analysis with application to the benzyl self-reaction |
| title_sort | combining synchrotron vacuum ultraviolet photoionization mass spectrometry and gas chromatography mass spectrometry for isomer specific mechanistic analysis with application to the benzyl self reaction |
| url | https://doi.org/10.1038/s41467-024-53889-9 |
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