Schumacher, Leon ; Pfeiffer, Johannes ; Shen, Jun ; Gutmann, Torsten ; Breitzke, Hergen ; Buntkowsky, Gerd ; Hofmann, Kathrin ; Hess, Christian (2024)
Collaborative Mechanistic Effects between Vanadia and Titania during the Oxidative Dehydrogenation of Propane Investigated by Operando and Transient Spectroscopy.
In: ACS Catalysis, 2023, 13 (12)
doi: 10.26083/tuprints-00028237
Artikel, Zweitveröffentlichung, Postprint
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Kurzbeschreibung (Abstract)
The oxidative dehydrogenation (ODH) of propane is of great technical importance, and supported VOₓ catalysts have shown promising properties for the reaction. One of the most prominent and active supports is titania, which exhibits a high activity but many questions regarding the catalyst system are still in debate. In this study, we elucidate the mechanism of the propane ODH reaction over VOₓ/TiO₂, using P25 and ALD (atomic layer deposition) synthesized TiO₂/SBA-15 as a support, with X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), ⁵¹V solid-state (ss)NMR, operando multiwavelength Raman, operando UV–vis, and transient IR spectroscopies. Bare titania shows a small conversion, leading to carbon formation, and the reaction occurs at the interface between anatase and rutile. In comparison, in VOₓ/TiO₂ catalysts, the activity shifts from titania to vanadia sites. UV-Raman spectroscopy and structural characterization data revealed the reaction to involve preferentially the V═O bonds of dimeric species rather than doubly bridged V–O–V bonds, which leads to higher propene selectivities. The active vanadium site shows a nuclearity-dependent behavior; that is, at higher loadings, when oligomeric vanadia is present, it shifts from V═O bonds to linear V–O–V bonds in oligomers, leading to less selective oxidation due to the better reducibility. Our operando/transient spectroscopic results demonstrate the direct participation of the titania support in the reaction by influencing the degree of vanadia oligomerization and enabling rapid hydrogen transfer from propane to vanadia via Ti–OH groups on anatase, accelerating the rate-determining step of the initial C–H bond breakage. The broader applicability of the results is confirmed by the behavior of the ALD-synthesized sample, which resembles that of P25. Our results highlight the detailed level of mechanistic understanding accessible from multiple spectroscopic approaches, which can be readily transferred to other materials and/or reactions.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2024 |
| Autor(en): | Schumacher, Leon ; Pfeiffer, Johannes ; Shen, Jun ; Gutmann, Torsten ; Breitzke, Hergen ; Buntkowsky, Gerd ; Hofmann, Kathrin ; Hess, Christian |
| Art des Eintrags: | Zweitveröffentlichung |
| Titel: | Collaborative Mechanistic Effects between Vanadia and Titania during the Oxidative Dehydrogenation of Propane Investigated by Operando and Transient Spectroscopy |
| Sprache: | Englisch |
| Publikationsjahr: | 6 Dezember 2024 |
| Ort: | Darmstadt |
| Publikationsdatum der Erstveröffentlichung: | 2 Juni 2023 |
| Ort der Erstveröffentlichung: | Washington, DC |
| Verlag: | American Chemical Society |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | ACS Catalysis |
| Jahrgang/Volume einer Zeitschrift: | 13 |
| (Heft-)Nummer: | 12 |
| Kollation: | 60 Seiten |
| DOI: | 10.26083/tuprints-00028237 |
| URL / URN: | https://tuprints.ulb.tu-darmstadt.de/28237 |
| Zugehörige Links: | |
| Herkunft: | Zweitveröffentlichungsservice |
| Kurzbeschreibung (Abstract): | The oxidative dehydrogenation (ODH) of propane is of great technical importance, and supported VOₓ catalysts have shown promising properties for the reaction. One of the most prominent and active supports is titania, which exhibits a high activity but many questions regarding the catalyst system are still in debate. In this study, we elucidate the mechanism of the propane ODH reaction over VOₓ/TiO₂, using P25 and ALD (atomic layer deposition) synthesized TiO₂/SBA-15 as a support, with X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), ⁵¹V solid-state (ss)NMR, operando multiwavelength Raman, operando UV–vis, and transient IR spectroscopies. Bare titania shows a small conversion, leading to carbon formation, and the reaction occurs at the interface between anatase and rutile. In comparison, in VOₓ/TiO₂ catalysts, the activity shifts from titania to vanadia sites. UV-Raman spectroscopy and structural characterization data revealed the reaction to involve preferentially the V═O bonds of dimeric species rather than doubly bridged V–O–V bonds, which leads to higher propene selectivities. The active vanadium site shows a nuclearity-dependent behavior; that is, at higher loadings, when oligomeric vanadia is present, it shifts from V═O bonds to linear V–O–V bonds in oligomers, leading to less selective oxidation due to the better reducibility. Our operando/transient spectroscopic results demonstrate the direct participation of the titania support in the reaction by influencing the degree of vanadia oligomerization and enabling rapid hydrogen transfer from propane to vanadia via Ti–OH groups on anatase, accelerating the rate-determining step of the initial C–H bond breakage. The broader applicability of the results is confirmed by the behavior of the ALD-synthesized sample, which resembles that of P25. Our results highlight the detailed level of mechanistic understanding accessible from multiple spectroscopic approaches, which can be readily transferred to other materials and/or reactions. |
| Freie Schlagworte: | propane ODH, Vanadia, Titania, Transient IR Spectroscopy, Operando Spectroscopy, Nuclearity Dependence, Support Interaction |
| Status: | Postprint |
| URN: | urn:nbn:de:tuda-tuprints-282378 |
| Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Fachbereich(e)/-gebiet(e): | 07 Fachbereich Chemie 07 Fachbereich Chemie > Eduard Zintl-Institut > Fachgebiet Anorganische Chemie 07 Fachbereich Chemie > Eduard Zintl-Institut 07 Fachbereich Chemie > Eduard Zintl-Institut > Fachgebiet Physikalische Chemie |
| Hinterlegungsdatum: | 06 Dez 2024 13:33 |
| Letzte Änderung: | 09 Dez 2024 12:42 |
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- Collaborative Mechanistic Effects between Vanadia and Titania during the Oxidative Dehydrogenation of Propane Investigated by Operando and Transient Spectroscopy. (deposited 06 Dez 2024 13:33) [Gegenwärtig angezeigt]
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