CO2 METHANATION UNDER TRANSIENT AND STEADY-STATE CONDITIONS OVER RH CEO2 AND CEO2-PROMOTED RH/SIO2 - THE ROLE OF SURFACE AND BULK CERIA/

A series of Rh/SiO2 samples promoted with CeO2 have been prepared and used as catalyst in CO2 methanation. Their behaviour has been compared to that of unpromoted Rh/SiO2 and Rh/CeO2 catalysts. The activity has been monitored under transient and steady-state conditions and the ca talysts have been characterized using quantitative temperature program med reduction, chemisorption, X-ray diffraction, and transmission elec tron microscopy. By impregnation of amorphous silica with Ce(NO3)(3). 6H(2)O followed by calcination at 923 K, aggregates of CeO2 particles with size ranging from 35 to 150 nm (depending on initial cerium loadi ng) form on the surface. These large agglomerates are constituted by i ndividual, smaller (5-15 nm), crystalline CeO2 particles. Redispersion of CeO2 in the presence of Ha at 773 K is observed in all samples. Th e presence of Rh, deposited by impregnation from RhCl3.3H(2)O solution s, accelerates the process. The reducibility of ceria is strongly enha nced by deposition on silica: complete reduction to Ce2O3 is observed for CeO2-supported samples at temperatures lower than 1100 K, while a maximum of 50% reduction (corresponding to CeO1.75) is observed far un supported CeO2 in the range of temperature 295-1400 K. The activity of the virgin catalyst, as tested under unsteady-state conditions, is po sitively influenced by the reduction temperature and CeO2 crystallite size. We suggest that the observed enhancement of catalytic activity i s linked to the presence of bulk. vacancies created on ceria after red uction at high temperatures. Annihilation of these oxygen vacancies by oxygen from CO2, under reaction conditions, restores the normal catal ytic behaviour. (C) 1995 Academic Press, Inc.