at Google ScholarTitle data
Delgado, Daniel ; Koch, Gregor ; Jiang, Shan ; Dong, Jinhu ; Kröhnert, Jutta ; Schmidt, Franz-Philipp ; Lunkenbein, Thomas ; Galdeano Ruano, Carmen ; Gaona-Miguélez, José ; Troya, Diego ; Oña-Burgos, Pascual ; Trunschke, Annette:
Low-Temperature Exsolution of Rh from Mixed ZnFeRh Oxides toward Stable and Selective Catalysts in Liquid-Phase Hydroformylation.
In: Journal of the American Chemical Society.
Vol. 147
(2025)
Issue 7
.
- pp. 5887-5903.
ISSN 1520-5126
DOI: https://doi.org/10.1021/jacs.4c14839
Abstract in another language
The exsolution of metal nanoparticles offers a promising strategy to enhance catalyst stability and fine-tune metal-support interactions. Expanding the use of exsolved nanoparticles in heterogeneous catalysis requires the development of low-temperature (T < 400 degrees C) exsolution processes. In this study, we report the synthesis of phase-pure ZnFe2-xRhxO4 metal oxide precursors with a spinel-type crystal structure. The isomorphic substitution of Fe3+ in the host lattice by Rh3+ was confirmed by X-ray diffraction and Raman spectroscopy combined with DFT calculations. The hydrothermal synthesis method of the oxide precursors was specifically chosen so that very small oxide particles of 10-20 nm were obtained, which enabled the exsolution of Rh nanoparticles with a particle size of about 1 to 2 nm at temperatures below 200 degrees C in a hydrogen-containing atmosphere. Compared to a Rh catalyst prepared by conventional wet impregnation of ZnFe2O4, the catalysts obtained by low-temperature exsolution show superior properties in terms of selectivity toward aldehydes in the hydroformylation of 1-hexene in the liquid phase. In addition, there is no Rh loss due to leaching, which is the main challenge for heterogeneous Rh catalysts used in liquid phase reactions. The exceptionally strong metal-support interaction imparts unique nanostructures and electronic properties to the exsolved metal nanoparticles, as revealed by electron energy loss spectroscopy (EELS) and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The specific adsorption sites on the exsolved Rh particles lead to stronger metal-hydride and weaker metal-carbonyl bonds on the surface, steering the reaction pathway toward hydroformylation rather than olefin isomerization.
Further data
| Item Type: | Article in a journal |
|---|---|
| Refereed: | Yes |
| Additional notes: | WOS:001418032200001 |
| Institutions of the University: | Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry Faculties Faculties > Faculty of Biology, Chemistry and Earth Sciences Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Operando-Analytics of Electrochemical Energy Storage > Chair Operando-Analytics of Electrochemical Energy Storage - Univ.-Prof. Dr. Thomas Lunkenbein Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Operando-Analytics of Electrochemical Energy Storage |
| Result of work at the UBT: | No |
| DDC Subjects: | 500 Science > 540 Chemistry |
| Date Deposited: | 12 Jun 2025 07:16 |
| Last Modified: | 04 Jul 2025 11:31 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/93649 |