Growth, structure, and chemistry of 1B metal nanoclusters supported on TiO₂(110)

Cu, Ag, and Au nanoclusters dispersed on TiO2(110) surfaces are utilized in a wide variety of applications ranging from microelectronics to heterogeneous catalysis. The unique chemical reactivity of these clusters is largely dependent on their size, shape, spatial distribution, and interfacial interaction with the oxide support. This implies that atomic level control of these properties can offer great opportunities in the development of novel devices based on supported metal nanoclusters. It is therefore necessary to understand how formation and restructuring of these clusters alter their geometric and electronic characteristics. This thesis involves the development of a theoretical foundation for studying the growth, structure, and chemistry of Cu, Ag, and Au on TiO2(110) surfaces. Using density functional theory calculations, we have identified factors that control the chemical reactivity of these supported metal nanoclusters. First we investigated the electronic and geometric structures of the stoichiometric and reduced rutile TiO2(110) surfaces. Then we examined the surface chemistry of TiO2 towards gaseous CO and O2, as well as the structure and growth of 1B metal nanoclusters on TiO2(110). We also examined how the electronic and geometric properties of mixed metal nanoclusters, CuAun(n≤ 3), differ versus their single metal counterparts, Cum and Aum (m ≤ 4). Finally, we considered CO oxidation reactions on TiO2(110)-supported small Au clusters. While current experimental techniques are limited to providing complementary atomic-level real space information, first principles-based atomic level simulations greatly contribute to elucidating the fundamental behavior and properties of Cu, Ag, and Au nanoclusters on TiO2(110). First principles modeling has paved the way for new catalyst development by investigating how the geometric, electronic, and chemical properties of TiO2-supported 1B metal nanoclusters vary with surface defects, adsorbates, and metal dopants before valuable time and manpower is invested in experimental synthesis and characterization.