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Molecular and Ionic Adsorption on Metal-Solution Interface

Walter Savich

My project will provide new knowledge about the mechanism of the copper electrodeposition reaction. Specifically I would de able to assess the role played by the nature of the substrate (Pt(111) electrode) and by the anions of the electrolyte ( HSO4- and SO42-) on the rate of copper electrodeposition and on the crystallographic structure of the electrodeposited material. It is known that crystallographic direction of growth of the electrodeposited material is to a large extend determined by the two dimensional structure of the first monolayer deposited onto a foreign substrate. In turn, the structure of the first monolayer is influenced by the morphology of the substrate and by the coadsorption of the anions from the electrolyte used in electroplating. In my study I will use a Pt(111) single crystal electrode of well defined surface crystallography and will study how coadsorption of sulfate and bisulfate present in electrolyte influences ordering of the first monolayer of electrodeposited copper. To achieve this goals I will:

(i) determine composition of mixed monolayer formed by copper and coadsorbed bisulfate using chronocoulometric technique and thermodynamics of perfectly polarized electrode:

(ii) determine structure of the mixed monolayer using electrochemical STM and AFM imaging techniques.

Some preliminary results are shown below. Those are cyclic voltametry curves for the H2SO4/HClO4 solution with variable sulfuric acid concentration and Gibbs excess of bisulfate on the surface of Pt(111)

Another part of my project is devoted to the quantum chemical simulations of molecular and ionic species adsorption on the Au(111) and Pt(111) surface. In this part I will show why reorientation of pyridine with potential changes take place and will compare it to adsorption on mercury electrode and also adsorption of 4-CNpyridine on Au(111). And also I will show moving forces of coadsorption of bisulfate and copper ions on Pt(111) surface.