Single-atom catalysts (SACs) consist of a low coverage of isolated metal atoms dispersed on a metal substrate, called single-atom alloys (SAAs), or alternatively single metal atoms coordinated to oxygen atoms on an oxide support. We present the synthesis of a new type of Co₁Cu SAC centers on a Cu₂O(111) support by means of a site-selective atomic layer deposition technique. Isolated metallic Co atoms selectively coordinate to the native oxygen vacancy sites (Cu sites) of the reconstructed Cu₂O(111) surface, forming a Co₁Cu SAA with no direct Co- O_x bonds. The centers, here referred to as Co₁Cu hybrid SACs, are found to stabilize the active Cu⁺ sites of the low-cost Cu₂O catalyst that otherwise is prone to deactivation under reaction conditions. The stability of the Cu₂O(111) surface was investigated by synchrotron radiation-based ambient-pressure X-ray photoelectron spectroscopy under reducing CO environment. The structure and reduction reaction are modeled by density functional theory calculations, in good agreement with experimental results.

A new vibrational spectroscopy method aimed at the investigation of solid surfaces in ultrahigh vacuum, called “Surface Action Spectroscopy (SAS)”, is described and the first results are reviewed. This technique is based on ideas and experiments performed in the gas phase. A surface is exposed to a messenger species at low temperature. This messenger species is desorbed via absorption of tunable infrared light from a free-electron laser and the desorption rate of the messenger species is recorded via mass spectrometry. It is shown that the technique is extremely surface sensitive and we discuss the basic mechanisms of the technique. We show a feasibility study on a V2O3(0001) surface, where we know the surface structure. We then proceed to the example of iron oxide films to study the surface structure in parallel with calculations of the surface phonons, which allow us to confirm the surface structure of Fe3O4(111) to be Fetet terminated. It also provides evidence for the so-called biphase structure. To conclude, we discuss possibilities to apply the technique to interesting questions in model and real catalysis, since the technique may provide interesting information independent of long-range order of the sample.