NDLI: Several different charge transfer and Ce<sup>3+</sup> localization scenarios for Rh

Content Provider	Royal Society of Chemistry (RSC)
Author	Hermansson, Kersti Castleton, Christopher W. M. Lu, Zhansheng Yang, Zongxian
Copyright Year	2014
Abstract	We present DFT+U based electronic structure calculations in a p(3 × 3) slab supercell, for low coverages of atomically dispersed Rh interacting with the CeO2(111) surface, comparing Rh as an adatom, and as a dopant substituted into the surface layer. We find that, energetically, a Rh atom approaching a ceria(111) surface with both sparse O and Ce vacancies present strongly prefers to heal the Ce vacancies, but next it prefers to adsorb on a stoichiometric region rather than healing an O vacancy. In the adatom system, Rh is oxidized by electron transfer to a 4f orbital on one Ce ion in the surface layer, which is then nominally converted from Ce4+ → Ce3+ (i.e. Rh adatoms are single donors). We show that there are a number of different local minima, with Ce3+ localization at 1st, 2nd or 3rd nearest neighbour Ce sites. The second neighbour is the most stable, but all are close in energy. In the Rh-doped system (Rh replaces Ce), Rh is oxidized by charge transfer to neighbouring O atoms, and Rh doping leads to deep acceptor and donor states. Rh is not stable in the O sublattice. Moreover, based on vacancy formation energies, we find that oxygen vacancy formation is strongly enhanced in the vicinity of Rh dopants, but slightly suppressed in the vicinity of Rh adatoms.
Starting Page	2333
Ending Page	2345
Page Count	13
File Format	HTM / HTML PDF
ISSN	20507488
Volume Number	2
Issue Number	7
Journal	Journal of Materials Chemistry A
DOI	10.1039/c3ta11169e
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Rh Supercell Adatom Dopant Cerium(IV) oxide Stoichiometry Ion Oxygen
Content Type	Text
Resource Type	Article
Subject	Chemistry Renewable Energy, Sustainability and the Environment Materials Science

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