Formic acid adsorption and decomposition on clean and atomic oxygen pre-covered Cu(100) surfaces.

Formic acid adsorption and decomposition on clean Cu(100) and two atomic oxygen pre-covered Cu(100) surfaces have been studied using surface science techniques including scanning tunneling microscopy, low-energy electron diffraction, x-ray photoelectron spectroscopy, and infrared reflection-absorption spectroscopy. The two atomic oxygen pre-covered Cu(100) surfaces include an O-(22 ×2)R45° Cu(100) surface and an oxygen modified Cu(100) surface with a local O-c(2 × 2) structure. The results show that the O-(22 ×2)R45° Cu(100) surface is inert to the formic acid adsorption at 300 K. After exposing to formic acid at 300 K, bidentate formate formed on the clean Cu(100) and local O-c(2 × 2) area of the oxygen modified Cu(100) surface. However, their adsorption geometries are different, being vertical to the surface plane on the former surface and inclined with respect to the surface normal with an ordered structure on the latter surface. The temperature programmed desorption spectra indicate that the formate species adsorbed on the clean Cu(100) surface decomposes into H and CO when the sample temperature is higher than 390 K. Differently, the proton from scission of the C-H bond of formate reacts with the surface oxygen, forming HO on the oxygen modified Cu(100) surface. The CO signal starts increasing at about 370 K, which is lower than that on clean Cu(100), indicating that the surface oxygen affiliates formate decomposition. Combining all these results, we conclude that the surface oxygen plays a crucial role in formic acid adsorption and formate decomposition.