Understanding the role of supported Rh atoms and clusters during hydroformylation and CO hydrogenation reactions with in situ / operando XAS and DRIFT spectroscopy.

Autor:	Sarma BB; Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT) Engesserstraße 20 76131 Karlsruhe Germany.; Institute of Catalysis Research and Technology, KIT Hermann-von Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany.; Laboratoire de Chimie de Coordination (LCC), CNRS, Université de Toulouse, INPT, 205 route de Narbonne 31077 Toulouse Cedex 4 France., Neukum D; Institute of Catalysis Research and Technology, KIT Hermann-von Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany., Doronkin DE; Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT) Engesserstraße 20 76131 Karlsruhe Germany.; Institute of Catalysis Research and Technology, KIT Hermann-von Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany., Lakshmi Nilayam AR; Institute of Nanotechnology, KIT Hermann-von-Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany., Baumgarten L; Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT) Engesserstraße 20 76131 Karlsruhe Germany.; Institute of Catalysis Research and Technology, KIT Hermann-von Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany., Krause B; Institut für Photonenforschung und Synchrotronstrahlung (IPS), KIT Hermann-von-Helmholtz Platz 1 D-76021 Karlsruhe Germany bidyut-bikash.sarma@lcc-toulouse.fr bidyutbikash.sarma@toulouse-inp.fr., Grunwaldt JD; Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT) Engesserstraße 20 76131 Karlsruhe Germany.; Institute of Catalysis Research and Technology, KIT Hermann-von Helmholtz Platz 1 76344 Eggenstein-Leopoldshafen Germany.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2024 Jul 10; Vol. 15 (31), pp. 12369-12379. Date of Electronic Publication: 2024 Jul 10 (Print Publication: 2024).
DOI:	10.1039/d4sc02907k
Abstrakt:	Supported Rh single-atoms and clusters on CeO 2 , MgO, and ZrO 2 were investigated as catalysts for hydroformylation of ethylene to propionaldehyde and CO hydrogenation to methanol/ethanol with in situ / operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and X-ray absorption spectroscopy (XAS). Under hydroformylation reaction conditions, operando spectroscopic investigations unravel the presence of both single atoms and clusters and detected at first propanal and then methanol. We find that the formation of methanol is associated with CO hydrogenation over Rh clusters which was further confirmed under CO hydrogenation conditions at elevated pressure. The activity of catalysts synthesized via a precipitation (PP) method over various supports towards the hydroformylation reaction follows the order: Rh/ZrO 2 > Rh/CeO 2 > Rh/MgO. Comparing Rh/CeO 2 catalysts synthesized via different methods, catalysts prepared by flame spray pyrolysis (FSP) showed catalytic activity for the hydroformylation reaction at lower temperatures (413 K), whereas catalysts prepared by wet impregnation (WI) showed the highest stability. These results not only provide fundamental insights into the atomistic level of industrially relevant reactions but also pave the way for a rational design of new catalysts in the future. Competing Interests: The authors declare no conflicts of interest. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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