Metastable gallium hydride mediates propane dehydrogenation on H2 co-feeding
© 2024. The Author(s), under exclusive licence to Springer Nature Limited..
In heterogeneous catalysis, the catalytic dehydrogenation reactions of hydrocarbons often exhibit a negative pressure dependence on hydrogen due to the competitive chemisorption of hydrocarbons and hydrogen. However, some catalysts show a positive pressure dependence for propane dehydrogenation, an important reaction for propylene production. Here we show that the positive activity dependence on H2 partial pressure of gallium oxide-based catalysts arises from metastable hydride mediation. Through in situ spectroscopic, kinetic and computational analyses, we demonstrate that under reaction conditions with H2 co-feeding, the dissociative adsorption of H2 on a partially reduced gallium oxide surface produces H atoms chemically bonded to coordinatively unsaturated Ga atoms. These metastable gallium hydride species promote C-H bond activation while inhibiting deep dehydrogenation. We found that the surface coverage of gallium hydride determines the catalytic performance. Accordingly, benefiting from proper H2 co-feeding, the alumina-supported, trace additive-modified gallium oxide catalyst GaOx-Ir-K/Al2O3 exhibited high activity and selectivity at high propane concentrations.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:16 |
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| Enthalten in: |
Nature chemistry - 16(2024), 4 vom: 05. Apr., Seite 575-583 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Sun, Guodong [VerfasserIn] |
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| Anmerkungen: |
Date Revised 05.04.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1038/s41557-023-01392-x |
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| 520 | |a © 2024. The Author(s), under exclusive licence to Springer Nature Limited. | ||
| 520 | |a In heterogeneous catalysis, the catalytic dehydrogenation reactions of hydrocarbons often exhibit a negative pressure dependence on hydrogen due to the competitive chemisorption of hydrocarbons and hydrogen. However, some catalysts show a positive pressure dependence for propane dehydrogenation, an important reaction for propylene production. Here we show that the positive activity dependence on H2 partial pressure of gallium oxide-based catalysts arises from metastable hydride mediation. Through in situ spectroscopic, kinetic and computational analyses, we demonstrate that under reaction conditions with H2 co-feeding, the dissociative adsorption of H2 on a partially reduced gallium oxide surface produces H atoms chemically bonded to coordinatively unsaturated Ga atoms. These metastable gallium hydride species promote C-H bond activation while inhibiting deep dehydrogenation. We found that the surface coverage of gallium hydride determines the catalytic performance. Accordingly, benefiting from proper H2 co-feeding, the alumina-supported, trace additive-modified gallium oxide catalyst GaOx-Ir-K/Al2O3 exhibited high activity and selectivity at high propane concentrations | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Zhao, Zhi-Jian |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Lulu |e verfasserin |4 aut | |
| 700 | 1 | |a Pei, Chunlei |e verfasserin |4 aut | |
| 700 | 1 | |a Chang, Xin |e verfasserin |4 aut | |
| 700 | 1 | |a Chen, Sai |e verfasserin |4 aut | |
| 700 | 1 | |a Zhang, Tingting |e verfasserin |4 aut | |
| 700 | 1 | |a Tian, Kaige |e verfasserin |4 aut | |
| 700 | 1 | |a Sun, Shijia |e verfasserin |4 aut | |
| 700 | 1 | |a Zheng, Lirong |e verfasserin |4 aut | |
| 700 | 1 | |a Gong, Jinlong |e verfasserin |4 aut | |
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