(63h) Density Functional Study of Adsorbates and Cationic Metal/Ceria Surfaces

Deskins, N. A., Purdue University
Thomson, K. T., Purdue University
Phatak, A. A., Purdue University
Ribeiro, F. H., Purdue University

   Mx+/ceria catalysts
have recently been found to be active for several reactions1,2
including CO oxidation, water-gas shift, NO reduction, and hydrocarbon
oxidation. In particular the water-gas shift reaction has the potential to
remove CO from proton-exchange membrane (PEM) fuel cell streams. The cationic
metals experimentally studied include Cu, Au, Rh, Pd, and Pt. The exact
structure of the Mx+/ceria system is unknown, but one model suggested
is the substitution of a lattice Ce4+ ions with the dopant Mx+
ions. Using density functional theory (DFT) we modeled the substitution process
of Pt and Rh in order to better understand the cationic arrangement. We also
modeled the interactions of CO with Mx+/ceria surfaces and found
carbonate-like (CO3) species to arise upon

CO adsorption. Carbonate-like species were previously found to form on nondoped
ceria surfaces3. CO is a common molecule present during many
reactions, and thus understanding CO interactions with ceria-based catalysts is
essential for many kinetic models. We discuss the formation of the different CO
species on the doped surfaces and the relevance to the relevant catalytic
processes. We also examined the formation of hydroxyl species on the ceria
surface, which becomes important when H2O is present.

(1) Fu, Q.; Saltsburg, H.; Flytzani-Stephanopoulos, M. Science 2003, 301, 935.

(2) Bera, P.; Patil, K. C.; Jayaram, V.; Subbanna, G. N.; Hegde, M. S. Journal
of Catalysis 2000, 196, 293.

(3) Yang, Z. X.; Woo, T. K.; Hermansson, K. Chemical Physics Letters 2004, 396,