Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation
© 2018, The Author(s), under exclusive licence to Springer Nature Limited. MoO3 and Mo2C have emerged as remarkable catalysts for the selective hydrodeoxygenation (HDO) of a wide range of oxygenates at low temperatures (that is, ≤673 K) and H2 pressures (that is, ≤1 bar). Although both catalysts can...
| Main Authors: | , , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | English |
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Springer Science and Business Media LLC
2021
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| Online Access: | https://hdl.handle.net/1721.1/135080 |
| _version_ | 1826204856127324160 |
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| author | Murugappan, Karthick Anderson, Eric M Teschner, Detre Jones, Travis E Skorupska, Katarzyna Román-Leshkov, Yuriy |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Murugappan, Karthick Anderson, Eric M Teschner, Detre Jones, Travis E Skorupska, Katarzyna Román-Leshkov, Yuriy |
| author_sort | Murugappan, Karthick |
| collection | MIT |
| description | © 2018, The Author(s), under exclusive licence to Springer Nature Limited. MoO3 and Mo2C have emerged as remarkable catalysts for the selective hydrodeoxygenation (HDO) of a wide range of oxygenates at low temperatures (that is, ≤673 K) and H2 pressures (that is, ≤1 bar). Although both catalysts can selectively cleave C–O bonds, the nature of their active sites remains unclear. Here we used operando near-ambient pressure X-ray photoelectron spectroscopy to reveal important differences in the Mo 3d oxidation states between the two catalysts during the hydrodeoxygenation of anisole. This technique revealed that, although both catalysts featured a surface oxycarbidic phase, the oxygen content and the underlying phase of the material impacted the reactivity and product selectivity during the hydrodeoxygenation. MoO3 transitioned between 5+ and 6+ oxidation states during the operation, consistent with an oxygen-vacancy driven mechanism wherein the oxygenate is activated at undercoordinated Mo sites. In contrast, Mo2C showed negligible oxidation state changes during hydrodeoxygenation and maintained mostly 2+ states throughout the reaction. |
| first_indexed | 2024-09-23T13:02:28Z |
| format | Article |
| id | mit-1721.1/135080 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T13:02:28Z |
| publishDate | 2021 |
| publisher | Springer Science and Business Media LLC |
| record_format | dspace |
| spelling | mit-1721.1/1350802023-09-12T20:08:43Z Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation Murugappan, Karthick Anderson, Eric M Teschner, Detre Jones, Travis E Skorupska, Katarzyna Román-Leshkov, Yuriy Massachusetts Institute of Technology. Department of Chemical Engineering © 2018, The Author(s), under exclusive licence to Springer Nature Limited. MoO3 and Mo2C have emerged as remarkable catalysts for the selective hydrodeoxygenation (HDO) of a wide range of oxygenates at low temperatures (that is, ≤673 K) and H2 pressures (that is, ≤1 bar). Although both catalysts can selectively cleave C–O bonds, the nature of their active sites remains unclear. Here we used operando near-ambient pressure X-ray photoelectron spectroscopy to reveal important differences in the Mo 3d oxidation states between the two catalysts during the hydrodeoxygenation of anisole. This technique revealed that, although both catalysts featured a surface oxycarbidic phase, the oxygen content and the underlying phase of the material impacted the reactivity and product selectivity during the hydrodeoxygenation. MoO3 transitioned between 5+ and 6+ oxidation states during the operation, consistent with an oxygen-vacancy driven mechanism wherein the oxygenate is activated at undercoordinated Mo sites. In contrast, Mo2C showed negligible oxidation state changes during hydrodeoxygenation and maintained mostly 2+ states throughout the reaction. 2021-10-27T20:10:38Z 2021-10-27T20:10:38Z 2018 2019-09-10T18:44:37Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/135080 en 10.1038/S41929-018-0171-9 Nature Catalysis Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Springer Science and Business Media LLC other univ website |
| spellingShingle | Murugappan, Karthick Anderson, Eric M Teschner, Detre Jones, Travis E Skorupska, Katarzyna Román-Leshkov, Yuriy Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation |
| title | Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation |
| title_full | Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation |
| title_fullStr | Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation |
| title_full_unstemmed | Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation |
| title_short | Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation |
| title_sort | operando nap xps unveils differences in moo3 and mo2c during hydrodeoxygenation |
| url | https://hdl.handle.net/1721.1/135080 |
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