Tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis
Abstract Unveiling catalytic mechanisms at a molecular level aids rational catalyst design and selectivity control for process optimization. In this study, we find that the Brønsted acid site density of the zeolite catalyst efficiently controls the guaiacol catalytic pyrolysis mechanism. Guaiacol de...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-40179-z |
| _version_ | 1797769410415427584 |
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| author | Zeyou Pan Allen Puente-Urbina Syeda Rabia Batool Andras Bodi Xiangkun Wu Zihao Zhang Jeroen A. van Bokhoven Patrick Hemberger |
| author_facet | Zeyou Pan Allen Puente-Urbina Syeda Rabia Batool Andras Bodi Xiangkun Wu Zihao Zhang Jeroen A. van Bokhoven Patrick Hemberger |
| author_sort | Zeyou Pan |
| collection | DOAJ |
| description | Abstract Unveiling catalytic mechanisms at a molecular level aids rational catalyst design and selectivity control for process optimization. In this study, we find that the Brønsted acid site density of the zeolite catalyst efficiently controls the guaiacol catalytic pyrolysis mechanism. Guaiacol demethylation to catechol initiates the reaction, as evidenced by the detected methyl radicals. The mechanism branches to form either fulvenone (c-C5H4 = C = O), a reactive ketene intermediate, by catechol dehydration, or phenol by acid-catalyzed dehydroxylation. At high Brønsted acid site density, fulvenone formation is inhibited due to surface coordination configuration of its precursor, catechol. By quantifying reactive intermediates and products utilizing operando photoelectron photoion coincidence spectroscopy, we find evidence that ketene suppression is responsible for the fivefold phenol selectivity increase. Complementary fulvenone reaction pathway calculations, along with 29Si NMR-MAS spectroscopy results corroborate the mechanism. The proposed, flexible operando approach is applicable to a broad variety of heterogeneous catalytic reactions. |
| first_indexed | 2024-03-12T21:07:39Z |
| format | Article |
| id | doaj.art-0b93fc5bc22742109acb0c1c39b26d16 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-12T21:07:39Z |
| publishDate | 2023-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-0b93fc5bc22742109acb0c1c39b26d162023-07-30T11:20:20ZengNature PortfolioNature Communications2041-17232023-07-011411910.1038/s41467-023-40179-zTuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysisZeyou Pan0Allen Puente-Urbina1Syeda Rabia Batool2Andras Bodi3Xiangkun Wu4Zihao Zhang5Jeroen A. van Bokhoven6Patrick Hemberger7Paul Scherrer InstituteInstitute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH ZurichInstitute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH ZurichPaul Scherrer InstitutePaul Scherrer InstitutePaul Scherrer InstitutePaul Scherrer InstitutePaul Scherrer InstituteAbstract Unveiling catalytic mechanisms at a molecular level aids rational catalyst design and selectivity control for process optimization. In this study, we find that the Brønsted acid site density of the zeolite catalyst efficiently controls the guaiacol catalytic pyrolysis mechanism. Guaiacol demethylation to catechol initiates the reaction, as evidenced by the detected methyl radicals. The mechanism branches to form either fulvenone (c-C5H4 = C = O), a reactive ketene intermediate, by catechol dehydration, or phenol by acid-catalyzed dehydroxylation. At high Brønsted acid site density, fulvenone formation is inhibited due to surface coordination configuration of its precursor, catechol. By quantifying reactive intermediates and products utilizing operando photoelectron photoion coincidence spectroscopy, we find evidence that ketene suppression is responsible for the fivefold phenol selectivity increase. Complementary fulvenone reaction pathway calculations, along with 29Si NMR-MAS spectroscopy results corroborate the mechanism. The proposed, flexible operando approach is applicable to a broad variety of heterogeneous catalytic reactions.https://doi.org/10.1038/s41467-023-40179-z |
| spellingShingle | Zeyou Pan Allen Puente-Urbina Syeda Rabia Batool Andras Bodi Xiangkun Wu Zihao Zhang Jeroen A. van Bokhoven Patrick Hemberger Tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis Nature Communications |
| title | Tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis |
| title_full | Tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis |
| title_fullStr | Tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis |
| title_full_unstemmed | Tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis |
| title_short | Tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis |
| title_sort | tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis |
| url | https://doi.org/10.1038/s41467-023-40179-z |
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