To identify surface phases that could play a role for the epoxidation of ethylene on Ag catalysts we have studied the interaction of Ag( 111) with O-2 at elevated pressures. Experiments were performed using high-pressure scanning tunneling microscopy (STM) at temperatures between 450 and 480 K and O-2 pressures in the mbar range. Below p(O-2) similar to 1 mbar the surface largely showed the structure of bare Ag( 111). At p(O-2) above similar to 1 mbar the (4 x 4) O structure and the closely related ( 4 x 5 root 3) rect structure were observed. The findings confirm theoretical predictions that the ( 4 x 4) O structure is thermodynamically stable at the oxygen partial pressure of the industrial ethylene oxide synthesis. However, in other experiments only a rough, disordered structure was observed. The difference is caused by the chemical state of the STM cell that depends on the pretreatment and on previous experiments. The surface was further analyzed by X-ray photoelectron spectroscopy (XPS). Although these measurements were performed after sample transfer to ultra-high vacuum (UHV), so that the surface composition was modified, the two surface states could still be identified by the presence of carbonate or a carbonaceous species, and by the absence or presence of a high-binding energy oxygen species, respectively. It turns out that the ( 4 x 4) O structure only forms under extremely clean conditions, indicating that the ( 4 x 4) O phase and similar oxygen-induced reconstructions of the Ag( 111) surface are chemically unstable. Chemical reactions at the inner surfaces of the STM cell also complicate the detection of the catalytic formation of ethylene oxide.
