The interface between a two-dimensional(2D)atomic crystal and a metal surface can be regarded as a nanoreactor, in which molecule adsorption and catalytic reactions may occur. In this work, we demonstrate that oxygen intercalation and desorption occur at the interface between hexagonal boron nitride(h-BN) overlayer and Pt(111) surface by using near-ambient pressure X-ray photoelectron spectroscopy(NAP-XPS), photoemission electron microscopy, and low-energy electron microscopy.Furthermore, CO oxidation under the h-BN cover was also observed by NAP-XPS. The present results indicate that the nanospace under the 2D cover can be used for surface reactions, in which novel surface chemistry may be induced by the nanoconfinement effect.
Graphene layers are often exposed to gaseous environments in their synthesis and application processes, and interactions of graphene surfaces with molecules particularly H_2 and O_2 are of great importance in their physico-chemical properties. In this work, etching of graphene overlayers on Pt(111) in H_2 and O_2 atmospheres were investigated by in-situ low energy electron microscopy. Significant graphene etching was observed in 10^(-5) Torr H_2 above 1023 K, which occurs simultaneously at graphene island edges and interiors with a determined reaction barrier at 5.7 eV. The similar etching phenomena were found in 10.7 Torr O_2 above 973 K, while only island edges were reacted between 823 and 923 K. We suggest that etching of graphene edges is facilitated by Pt-aided hydrogenation or oxidation of edge carbon atoms while intercalation-etching is attributed to etching at the interiors at high temperatures. The different findings with etching in O_2 and H_2 depend on competitive adsorption, desorption, and diffusion processes of O and H atoms on Pt surface, as well as intercalation at the graphene/Pt interface.
