Abstract
Molecular-level simulation is increasingly a key complement to experiment in the exploration of metal oxide nanoparticle structure, composition, and reactivity. Density functional theory (DFT) in particular has emerged as the leading tool for these studies because of its balance of theoretical rigor and computational tractability. In this chapter the use of these tools to describe and explain chemical reactivity at oxide surfaces is explored. The model systems considered include comparisons of the adsorption chemistry of CO2, SOx, and NOx at base metal oxide surfaces, the facile hydration and resulting hydroxylated surface of alumina, the stability and reactivity of the RuO2 surface towards O2, and particle size effects on the stability of Pt oxide particles. The combination provides both an overview of the capabilities of current electronic structure methods as applied to metal oxides and an introduction to the opportunities for enhanced insight that comes from their use. This research is sponsored by the Office of Energy Efficiency and Renewable Energy of the U.S. Department of Energy and has been performed at Oak Ridge National Laboratory, which is managed by UT-Battelle, LLC, under DOE Contract No. DE-AC05-00OR22725.