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Distinct Physicochemical Properties of the First Ceria Monolayer on Cu(111)

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† Faculty of Mathematics and Physics, Charles University, V Holešovičkách 2, Praha 8, Czech Republic
‡ Theory@Elettra group, Istituto Officina dei Materiali, CNR-IOM DEMOCRITOS, s.s. 14 km 163,5 in AREA Science Park, I-34149 Trieste, Italy
§ SISSA, Scuola Internazionale Superiore di Studi Avanzati, via Bonomea 265, I-34136 Trieste, Italy
*E-mail: [email protected]
Cite this: J. Phys. Chem. C 2012, 116, 11, 6677–6684
Publication Date (Web):March 13, 2012
https://doi.org/10.1021/jp211955v
Copyright © 2012 American Chemical Society
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    Abstract

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    Discontinuous ceria layers on Cu(111) represent heterogeneous catalysts with notable activities in water–gas shift and CO oxidation reactions. Ultrathin ceria islands in these catalysts are composed of monolayers of ceria exhibiting CeO2(111) surface ordering and bulklike vertical stacking (O–Ce–O) down to a single ceria monolayer representing the oxide-metal interface. Scanning tunneling microscopy (STM) reveals marked differences in strain buildup and the structure of oxygen vacancies in this first ceria monolayer compared to thicker ceria layers on Cu(111). Ab-initio calculations allow us to trace back the distinct properties of the first ceria monolayer to pronounced finite size effects when the limiting thickness of the oxide monolayer and the proximity of metal substrate cause significant rearrangement of charges and oxygen vacancies compared to thicker and/or bulk ceria.

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