Inside ordered mesopores of ceria, thin silica overlayers were formed on the ceria surface, which can make alkali metal cations highly dispersed as Si-O-(alkali metal)(+). When nanoparticles of Rh were impregnated into these modified ceria mesopores, unique tilted CO adsorption sites (Rh-C=O -alkali metal(+)) wereformed, which might stabilize reaction intermediates of C-2 oxygenated compounds and which might enhance their selective formation in CO-H-2 reaction under mild conditions. (C) 2014 Elsevier B.V. All rights reserved.