X-RAY PHOTOELECTRON DIFFRACTION STUDY OF A LONG-RANGE-ORDERED ACETATE LAYER ON Ni(110)

Abstract

An investigation of acetic acid adsorption on Ni(110) at room temperature by LEED and X-ray photoelectron diffraction reveals a well-ordered c(2 × 2) acetate overlayer with a molecular coverage near 0.5. Large solid angle maps of angle-resolved C 1s and O 1s intensities from this layer show intense maxima due to electron forward scattering by nearby atoms, either of the same acetate or of neighboring acetate species. The data provide strong evidence for acetate in a bidentate configuration, bonded through both oxygen atoms to the surface and aligned along the [110] surface azimuth. A real space model for the c(2 × 2) acetate layer has been derived and single scattering cluster calculations for this model layer have been carried out for C 1s and O 1s emissions. Allowing for changes in intramolecular bond length of the acetate relative to those in a Ni-acetate complex, good agreement between experimental and theoretical C 1s and O 1s distributions was obtained.

Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface

“…Interestingly, condensed carboxylate layers have been observed on other surfaces. A dense c(2 × 2) acetate structure was reported previously for Cu(110) (refs 24 , 26 ) and Ni(110) (refs 27 , 28 ). However, the driving force for assembly and metal atom incorporation—in a somewhat different fashion than for acetate on Au(110)—was not investigated in the mentioned studies.…”

“…2e ), consistently with ∼ 0.25 ML coverage deduced from the initial O coverage. The c(2 × 2) acetate structure has been reported on Cu(110) (refs 23 , 24 , 25 , 26 ) and Ni(110) (refs 27 , 28 ) and the molecule adsorption geometry is bidentate top, with the two oxygen atoms in acetate binding to two topmost Au atoms along the close packed rows. Our DFT calculations show the same preferred adsorption geometry on Au(110) ( Supplementary Fig.…”

Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110)

“…The effect of carboxylate islanding is not unique to gold 43 , 54 but rather has been shown to occur generally on metal surfaces, including: Cu, 55 – 59 Ag, 60 Al, 60 Ni 61 , 62 and Pd. 63 , 64 Therefore, we anticipate that the effect of intermolecular interactions on carboxylate stability demonstrated herein would be a necessary consideration to carboxylate-metal systems.…”

Adsorption of Acetate on Au(111): An in‐situ Scanning Tunnelling Microscopy Study and Implications on Formic Acid Electrooxidation

“…For an Au(110) surface, a densely‐packed c (2×2) structure of acetate, with a coverage of 0.25 ML, was identified . A c (2×2) acetate structure has also been reported for Ni(110), and for Cu(110) . Under electrochemical conditions, however, interactions of adsorbed molecules are altered.…”