Unique active site structure for C2 oxygenated compound formation in CO–H2 reaction over ordered mesoporous CeO2 supported Rh catalysts

•Ordered mesoporous ceria is an excellent support in Rh catalyzed CO–H2 reactions.•Inside mesopores, SiO2 layers are formed. They disperse alkali metal cations well.•A unique Rh-LiOSi structure stabilizes C2-oxygenated intermediates as a tilted form.•The C2-oxygenate selectivity is enhanced under mild conditions.

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 (RhCOalkali metal+) were formed, which might stabilize reaction intermediates of C2 oxygenated compounds and which might enhance their selective formation in CO–H2 reaction under mild conditions.

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