CO Oxidation at the Interface between Doped CeO2 and Supported Au Nanoclusters.

DFT+U calculations of CO oxidation by Au13 nanoclusters (NCs) supported on either CeO2 or doped (X-Ce)O2 (X = Au, Pt, Pd, Ti, Ru, Zr) show that doping the CeO2 support accelerates CO oxidation by the Mars-van Krevelen mechanism at the Au-(X-Ce)O2 interface. We find that Au, Pd, Pt, and Ti dopants significantly lower the vacancy formation energy of the CeO2 support and that electron donation from the supported Au13 NC shifts the vacancy formation energy of (X-Ce)O2 and determines the final vacancy formation energy of Au13@(X-Ce)O2. The vacancy formation energy of Au13@(X-Ce)O2 is a good reactivity descriptor for CO oxidation at the Au-(X-Ce)O2 interface and a screening factor for dopant selection. Our results confirm that the catalytic activity of oxide-supported Au catalysts can be modified by the chemical composition of the support and suggest that chemical modification of the oxide support is promising for the optimization of oxidation catalysis by supported Au NCs/nanoparticles.