Thiol adsorption on metal oxide nanoparticles

. Density functional theory (DFT) calculations were performed using small metal oxide clusters, assuming that dissociative adsorption occurs by replacement of a hydroxyl group attached to a metal site and the formation of water. The theoretical and experimental results generally agree, suggesting that this is indeed the adsorption mechanism for most of the nanoparticles. The agreement also suggests that the size and geometry of the nanoclusters play a minor role and that the relative strengths of the metal-sulfur and metal-hydroxyl bonds dictate thiol adsorption. This work has important implications related to the functionalization of metal oxide nanoparticles and surfaces.