Published August 27, 2020 | Version v1
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Vibrational frequencies of cerium oxide-bound CO: a challenge for conventional DFT methods

  • 1. Institute of Physics Rosario, IFIR, National Scientific and Technical Research Council, CONICET, and National University of Rosario, UNR, S2000EKF Rosario, Santa Fe, Argentina
  • 2. Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain
  • 3. Institute of Catalysis Research and Technology, IKFT, Karlsruhe Institute of Technology, KIT, 76344 Eggenstein-Leopoldshafen, Germany
  • 4. Institute of Functional Interfaces, IFG, Karlsruhe Institute of Technology, KIT, 76344 Eggenstein-Leopoldshafen, Germany

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Description

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 CeO2 (110) and (111) surfaces and show that the commonly applied DFT(PBE)+U method does not provide reliable CO vibrational frequencies by comparing with state-of-the-art infrared spectroscopy experiments for monocrystalline CeO2 surfaces. Good agreement requires the hybrid DFT approach with the HSE06 functional. The failure of conventional 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 C-O 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.

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References

Journal reference
P. G. Lustemberg, P. Pleßow, Y. Wang, C. Yang, A. Nefedov, F. Studt, C. Wöll, M. V. Ganduglia-Pirovano, Phys. Rev. Lett 125, 256101 (2020), doi: 10.1103/PhysRevLett.125.256101