Abstract
The interplay between the metal-support interaction and stability with respect to sintering has been investigated for Pt nanoparticles supported on well-ordered Co3O4(111)/Ir(100) films in UHV and under oxidizing conditions by means of synchrotron radiation photoelectron spectroscopy (SRPES) and near ambient pressure X-ray photoelectron spectroscopy (NAP XPS). The electronic metal-support interaction between Pt and Co3O4(111) associated with charge transfer results in partial reduction of Co3O4(111) yielding partially oxidized Pt+ species at the interface.
The stability of the supported Pt particles is coupled with the oxidation state of Pt+ species, which can be reduced or oxidized depending on the Pt coverage and reactive environment. Annealing of Pt/Co3O4(111)/Ir(100) in UHV triggers the reduction of Pt+ species.
At higher temperature, reverse spillover of oxygen to the Pt nanoparticles is accompanied by reduction of Co3O4(111). Under these conditions, the oxidation state of Pt+ species depends strongly on Pt coverage.
Thus, at low Pt coverage (0.3 ML Pt), Pt+ is converted to Pt4+, at intermediate coverage (1.3 ML Pt), Pt+ remains stable, and at high Pt coverage (1.93 ML), Pt+ is reduced to Pt-0. Sintering of Pt particles is associated with the reduction of the Pt+ species.
This process is prevented under oxidizing conditions due to the formation of an interfacial oxide PtOx. The formation of an interfacial PtOx is observed at 300 K under exposure to 1 x 10(-6) mbar O-2 at Pt coverages below 1.3 ML.
Using NAP XPS, we observe the formation of an interfacial PtOx at high Pt coverage (2.0 ML) in an oxygen atmosphere (1 mbar) at 300 K while the formation of surface PtOx is kinetically hindered and occurs above 550 K only.