A comparative DFT study of adsorption and catalytic performance of Au nanoparticles at anatase and brookite TiO2 surfaces

We have compared the adsorption properties of small Aun (n = 1-8) nanoparticles on the defect-free (stoichiometric) and defective (partially reduced) brookite TiO2(210) and anatase TiO2(101) surfaces using density functional theory calculations. The interaction between Au atoms and anatase TiO2(101) was determined to be quite weak and small Aun particles grown at defects (O vacancies) prefer extended 2D structures. By contrast, dispersion and 3D configurations appear to be favored at brookite TiO2(210) for Aun nanoparticles due to their strong interaction. Calculations of CO oxidation at Aun (n = 6-8) particles supported at defective brookite TiO2(210) show that occurrence of protruding low-coordinated Au atoms is essential for favorable CO adsorption and subsequent reaction with O2. In particular, the configuration of the Aun nanoparticles can determine the energetics in the formation of active Au atoms, and their mobility also affects the reaction between CO and O2 (or O).

Research Highlights► We calculate Au nanoparticles at two TiO2 surfaces. ► We compare the structures and catalytic activities of Au nanoparticles. ► Au nanoparticles like to grow at O vacancies of brookite (210) and anatase (101). ► 3D Au nanoparticles like to form at brookite (210). ► 3D Au nanoparticles are highly active for CO and O2 adsorption and reaction.