Dispersion and stability mechanism of Pt nanoparticles on transition-metal oxides

The heterogeneous catalysts of Pt/transition-metal oxides are typically synthesized through calcination at 500 °C, and Pt nanoparticles are uniformly and highly dispersed when hydrogen peroxide (H₂O₂) is applied before calcination. The influence of H₂O₂ on the dispersion and the stability of Pt nanoparticles on titania-incorporated fumed silica (Pt/Ti–FS) supports was examined using X-ray absorption fine structure (XAFS) measurements at the Pt L₃ and Ti K edges as well as density functional theory (DFT) calculations. The local structural and chemical properties around Pt and Ti atoms of Pt/Ti–FS with and without H₂O₂ treatment were monitored using in-situ XAFS during heating from room temperature to 500 °C. XAFS revealed that the Pt nanoparticles of H₂O₂-Pt/Ti–FS are highly stable and that the Ti atoms of H₂O₂-Pt/Ti–FS support form into a distorted-anatase TiO₂. DFT calculations showed that Pt atoms bond more stably to oxidized–TiO₂ surfaces than they do to bare- and reduced–TiO₂ surfaces. XAFS measurements and DFT calculations clarified that the presence of extra oxygen atoms due to the H₂O₂ treatment plays a critical role in the strong bonding of Pt atoms to TiO₂ surfaces.