RESUMEN
Aberration-corrected transmission electron microscopy and high-angle annular dark field imaging was used to investigate the surface structures and internal defects of CeO2 nanoparticles (octahedra, rods, and cubes). Further, their catalytic reactivity in the water-gas shift (WGS) reaction and the exposed surface sites by using FTIR spectroscopy were tested. Rods and octahedra expose stable (111) surfaces whereas cubes have primarily (100) facets. Rods also had internal voids and surface steps. The exposed planes are consistent with observed reactivity patterns, and the normalized WGS reactivity of octahedra and rods were similar, but the cubes were more reactive. In situ FTIR spectroscopy showed that rods and octahedra exhibit similar spectra for -OH groups and that carbonates and formates formed upon exposure to CO whereas for cubes clear differences were observed. These results provide definitive information on the nature of the exposed surfaces in these CeO2 nanostructures and their influence on the WGS reactivity.
Asunto(s)
Monóxido de Carbono/química , Cerio/química , Microscopía Electrónica de Transmisión , Nanopartículas/química , Agua/química , Adsorción , Hidrógeno/química , Propiedades de Superficie , TemperaturaRESUMEN
A mechanism of CO oxidation by a thin surface oxide of Rh supported on ceria is proposed: CO is oxidized by the Rh-oxide film, which is subsequently reoxidized by a ceria surface O atom. The proposed mechanism is supported by in situ Raman spectroscopic investigations.