Role of dopant in the formation of reactive oxygen species and oxidation catalysis on CeO2(1 1 1)

Document Type

Article

Publication Date

1-1-2024

Abstract

We theoretically investigate the role of nine 3d–5d Groups 9–11 metals substitutionally doped into CeO2(1 1 1) in terms of i) oxygen vacancy (VO) formation; ii) H and CO adsorption; iii) H2 oxidation, C3H8 oxidative dehydrogenation, and CO oxidation. Lattice O and O2 species at the doped sites are significantly more active toward binding H and CO than in un-doped CeO2(1 1 1). All the dopants lower the VO formation energy vs. un-doped CeO2(1 1 1), which becomes negative for Ni, Pd, Pt, Cu, and Ag. The square planar structure is energetically preferred by all the doped VO. Whether doping promotes the catalysis of the oxidation reactions depends on which of the chemisorption, VO formation, and surface re-oxidation steps is the bottleneck. When the VO formation step is, doping is expected to have little promotional effect, because VO formation is an iso-reduction step whose reaction energy is independent of doping.

Publication Source (Journal or Book title)

Journal of Catalysis

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