Physical confinement versus adsorption driven reconstruction: The case of sulfate anion interaction with vicinal Cu(111) surfaces

Nano-electrochemistry, i.e., the research of the properties of nano-(structured) electrodes and their influence on electrochemical processes when immersed inside an electrolyte, represents a hot topic in view of applications in nano-electronics, electro-catalysis and energy storage devices. The role of physical confinement in the electrochemical fabrication and performances of the respective systems have been recently addressed in the context of metal-organic networks on surfaces, but rarely of nano-structured bare metal surfaces, for instance, regularly stepped (vicinal) surfaces. In this work we investigate the interplay between physical confinement and adsorbate induced restructuring by the electrochemical adsorption of sulfate anions on the flat and two distinctly different vicinal Cu(111) surfaces. Sulfate adsorption on the flat Cu(111) surface is known to create a long-range ordered Moiré-superstructure with lattice parameters in the 2–4 nm range due to an expansion of the topmost layer of copper atoms with respect to the underlying crystal planes. This restructuring is also observed on a vicinal Cu(111) surface whose original terrace width is considerably smaller than the lattice vectors of the sulfate induced Moiré-structure. The results clearly indicate not only that the Moiré formation lifts the physical confinement imposed by the initial terrace width, but also shine more light on the Moiré formation process itself. Such adsorbate induced restructuring, of course, depends on the respective adsorbate – electrode combination, but must, in principle, always be taken into account in order to understand electrochemical processes at nano-structured (and nano-sized) electrode surfaces.