(81g) Mechanistic Study of CO Oxidation On Supported Gold Nanoparticles: How Nanoparticle Restructuring Impacts Reaction Energetics

Titania supported gold nanoclusters have been shown to exhibit unique catalytic activity for the room temperature oxidation of CO to CO₂.  Detailed experimental studies have shown that the gold nanoparticles routinely reorganize into different conformational arrangements during reaction.  However, to-date no experimental or computational mechanistic studies have shown how this restructuring influences the overall energetics for the CO oxidation reaction.  The results of this combined DFT and ReaxFF study examine how gold particle restructuring influences the overall energetics for the oxidation reactions.  Specifically, reactive force field (ReaxFF) models were used to identify promising gold cluster structures that contained adsorbed intermediates for the CO oxidation reaction.  Promising structures were later examined in greater detail using ab initio (DFT) techniques.  The final energy minimized structures were then used to calculate reaction energetics and transition state energies.  The resulting information was ultimately incorporated into a microkinetics model to examine how gold cluster restructuring influences the overall reaction rate.