WP3.Theoretical Modeling

D.3.1 Theoretical characterization of a supported tailored cluster in Month 20

Theoretical characterization of small Agn and Aun (n=1,4) clusters supported on regular and defective a-TiO2 and t-ZrO2 (101) surfaces have been successfully completed using DFT+U (D 3.1).
The effect of intrinsic and extrinsic defects of titania on the metal-support interaction as well as the effect of oxygen vacancies, N and Nb doping on the binding nature of small metal clusters on the titania surface has been investigated. Defects and dopants create new states in the band gap of titania giving rise to charge transfer. Dopants and oxygen vacancies in ZrO2 modifies the metal-support interaction improving the catalytic properties of the metal by changing the electronic structure and charge. In the nanostructure regime, ZrO2 nanoparticles show special electronic structure due to undercoordination that is tunable with size and shape offering the possibility to improve the catalytic
properties as a metal support.