TY  - JOUR
AU  - Sarma, Bidyut Bikash
AU  - Neukum, Dominik
AU  - Doronkin, Dmitry
AU  - Lakshmi Nilayam, Ajai Raj
AU  - Baumgarten, Lorena
AU  - Krause, Baerbel
AU  - Grunwaldt, Jan-Dierk
TI  - Understanding the role of supported Rh atoms and clusters during hydroformylation and CO hydrogenation reactions with in situ / operando XAS and DRIFT spectroscopy
JO  - Chemical science
VL  - 15
IS  - 31
SN  - 2041-6520
CY  - Cambridge
PB  - RSC
M1  - PUBDB-2024-05033
SP  - 12369-12379
PY  - 2024
AB  - 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. 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. 
LB  - PUB:(DE-HGF)16
C6  - pmid:39118611
UR  - <Go to ISI:>//WOS:001275391000001
DO  - DOI:10.1039/D4SC02907K
UR  - https://bib-pubdb1.desy.de/record/611720
ER  -