by Julien Scalbert, Cecile Daniel, Yves Schuurman, Cyril Thomas, Frederic C. Meunier
in Journal of Catalysis
Volume 318, October 2014, Pages 61–66
• The deactivating sites over Rh/alumina in the presence of CO2 during toluene hydrogenation at 348 K were identified.
• Using a less dispersed Rh supported on silica enabled obtaining a catalyst leading to no carbonyl poisoning.
• Toluene was shown to readily displace any CO adsorbed on Rh on our Rh/SiO2 at 348 K.
Rhodium highly dispersed on alumina becomes partly poisoned by strongly bound CO when used for toluene hydrogenation at 348 K in the presence of CO2. Operando FT-IR analysis enabled to observed CO(ads) build up over the sample, while no CO(gas) could be measured in the reactor effluent. Analyses carried out by complementary operando and in situ infrared spectroscopy studies unraveled the nature of the deactivating sites, i.e. low coordination number Rh sites located at the interface with the alumina support basic sites on which CO2 strongly adsorbs. Rh supported on silica with a lower dispersion remained free of adsorbed carbon monoxide even under higher CO2 pressures, stressing the relevance of infrared studies in catalyst rational design.
Rhodium; IR spectroscopy; Hydrogenation; Carbon dioxide