Understanding the role of supported Rh atoms and clusters during hydroformylation and CO hydrogenation reactions with in situ / operando XAS and DRIFT spectroscopy
Sarma, Bidyut Bikash 1,2; Neukum, Dominik 1; Doronkin, Dmitry E.
1,2; Lakshmi Nilayam, Ajai Raj 3; Baumgarten, Lorena 1,2; Krause, Bärbel
4; Grunwaldt, Jan-Dierk
1,2
1 Institut für Katalyseforschung und -technologie (IKFT), Karlsruher Institut für Technologie (KIT)
2 Institut für Technische Chemie und Polymerchemie (ITCP), Karlsruher Institut für Technologie (KIT)
3 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)
4 Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie (KIT)
1,2; Lakshmi Nilayam, Ajai Raj 3; Baumgarten, Lorena 1,2; Krause, Bärbel
4; Grunwaldt, Jan-Dierk
1,21 Institut für Katalyseforschung und -technologie (IKFT), Karlsruher Institut für Technologie (KIT)
2 Institut für Technische Chemie und Polymerchemie (ITCP), Karlsruher Institut für Technologie (KIT)
3 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)
4 Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie (KIT)
Abstract:
Supported Rh single-atoms and clusters on CeO2, MgO, and ZrO2 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/ZrO2 > Rh/CeO2 > Rh/MgO. Comparing Rh/CeO2 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. ... mehr
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/ZrO2 > Rh/CeO2 > Rh/MgO. Comparing Rh/CeO2 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. ... mehr
| Zugehörige Institution(en) am KIT | Institut für Katalyseforschung und -technologie (IKFT) Institut für Nanotechnologie (INT) Institut für Photonenforschung und Synchrotronstrahlung (IPS) Institut für Technische Chemie und Polymerchemie (ITCP) Karlsruhe Nano Micro Facility (KNMF) |
| Publikationstyp | Zeitschriftenaufsatz |
| Publikationsdatum | 07.08.2024 |
| Sprache | Englisch |
| Identifikator | ISSN: 2041-6520, 2041-6539 KITopen-ID: 1000172365 |
| HGF-Programm | 38.03.02 (POF IV, LK 01) Power-based Fuels and Chemicals |
| Weitere HGF-Programme | 56.12.11 (POF IV, LK 01) Materials - Quantum, Complex and Functional |
| Erschienen in | Chemical Science |
| Verlag | Royal Society of Chemistry (RSC) |
| Band | 15 |
| Heft | 31 |
| Seiten | 12369–12379 |
| Vorab online veröffentlicht am | 11.07.2024 |
| Nachgewiesen in | Web of Science Dimensions Scopus |