Abstract
In ceria-based catalysis, the shape of the catalyst particle, which determines the exposed crystal facets, profoundly affects its reactivity. The vibrational frequency of adsorbed carbon monoxide (CO) can be used as a sensitive probe to identify the exposed surface facets, provided reference data on well-defined single crystal surfaces together with a definitive theoretical assignment exist. We investigate the adsorption of CO on the and (111) surfaces and show that the commonly applied method does not provide reliable CO vibrational frequencies by comparing with state-of-the-art infrared spectroscopy experiments for monocrystalline surfaces. Good agreement requires the hybrid DFT approach with the HSE06 functional. The failure of conventional density-functional theory (DFT) is explained in terms of its inability to accurately describe the facet- and configuration-specific donation and backdonation effects that control the changes in the bond length upon CO adsorption and the CO force constant. Our findings thus provide a theoretical basis for the detailed interpretation of experiments and open up the path to characterize more complex scenarios, including oxygen vacancies and metal adatoms.
- Received 27 May 2020
- Revised 4 September 2020
- Accepted 9 November 2020
DOI:https://doi.org/10.1103/PhysRevLett.125.256101
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