Electronic Metal-Support Interaction-Modified Structures and Catalytic Activity of CeOx Overlayers in CeOx /Ag Inverse Catalysts

Chemistry. 2019 Dec 13;25(70):15978-15982. doi: 10.1002/chem.201904134. Epub 2019 Nov 7.

Abstract

Electronic metal-support interactions (EMSIs) of oxide-supported metal catalysts strongly modifies the electronic structures of the supported metal nanoparticles. The strong influence of EMSIs on the electronic structures of oxide overlayers on metal nanoparticles employing cerium oxides/Ag inverse catalysts is reported herein. Ce2 O3 overlayers were observed to exclusively form on Ag nanocrystals at low cerium loadings and be resistant to oxidation treatments up to 250 °C, whereas CeO2 overlayers gradually developed as the cerium loading increased. Ag cubes enclosed by {001} facets with a smaller work function exert a stronger EMSI effect on the CeOx overlayers than Ag cubes enclosed by {111} facets. Only the CeO2 overlayers with a fully developed bulk CeO2 electronic structure significantly promote the catalytic activity of Ag nanocrystals in CO oxidation, whereas cerium oxide overlayers with other electronic structures do not. These results successfully extend the concept of EMSIs from oxide-supported metal catalysts to metal-supported oxide catalysts.

Keywords: CO oxidation; X-ray photoelectron spectroscopy; charge transfer; electronic structures; strong metal-support interactions.