In situ coarsening study of inverse micelle-prepared Pt nanoparticles supported on gamma-Al2O3: pretreatment and environmental effects

The thermal stability of inverse micelle prepared Pt nanoparticles (NPs) supported on nanocrystalline gamma-Al2O3 was monitored in situ under different chemical environments (H-2, O-2, H2O) via extended X-ray absorption fine-structure spectroscopy (EXAFS) and ex situ via scanning transmission electron microscopy (STEM). Drastic differences in the stability of identically synthesized NP samples were observed upon exposure to two different pre-treatments. In particular, exposure to O-2 at 400 degrees C before high temperature annealing in H-2 (800 degrees C) was found to result in the stabilization of the inverse micelle prepared Pt NPs, reaching a maximum overall size after moderate coarsening of similar to 1 nm. Interestingly, when an analogous sample was pre-treated in H-2 at similar to 400 degrees C, a final size of similar to 5 nm was reached at 800 degrees C. The beneficial role of oxygen in the stabilization of small Pt NPs was also observed in situ during annealing treatments in O-2 at 450 degrees C for several hours. In particular, while NPs of 0.5 +/- 0.1 nm initial average size did not display any significant sintering (0.6 +/- 0.2 nm final size), an analogous thermal treatment in hydrogen leads to NP coarsening (1.2 +/- 0.3 nm). The same sample pre-dosed and annealed in an atmosphere containing water only displayed moderate sintering (0.8 +/- 0.3 nm). Our data suggest that PtOx species, possibly modifying the NP/support interface, play a role in the stabilization of small Pt NPs. Our study reveals the enhanced thermal stability of inverse micelle prepared Pt NPs and the importance of the sample pre-treatment and annealing environment in the minimization of undesired sintering processes affecting the catalytic performance of nanosized particles.