Coarsening-resistant Ag nanoparticles stabilized on amorphous TiOx nanoparticles

Bare Ag nanoparticles (∼10 nm) and Ag nanoparticles (1–20 nm) on the surfaces of larger TiOx nanoparticles were prepared by laser ablation of microparticle aerosols (LAMA). The behaviors of the nanoparticles during high temperature annealing were then studied with ex situ and in situ transmission electron microscopy. For the ex situ heating experiments, Ag and Ag-on-TiOx NPs were collected onto gold TEM grids and subjected to annealing treatments at 500 °C in argon, vacuum, and air. At this temperature, bare Ag NPs on carbon TEM supports coarsened rapidly in both air and argon atmospheres. In contrast, Ag-on-TiOx NPs that were heated to 500 °C in flowing argon or in a vacuum did not coarsen significantly and were remarkably stable. Ag-on-TiOx NPs that were heated to 500 °C in air, however, behaved quite differently. The TiOx crystallized upon heating and a significant loss of Ag were observed from the surfaces of the TiOx, likely due to sublimation. These results demonstrate that the surface defect structure and chemistry of the oxide support strongly influence the thermal stability of Ag NPs produced by LAMA.