The Interaction of Water with Solid Surfaces: Fundamental Aspects Revisited

Ordered anion adlayers on metal electrode surfaces.

Nitrate adsorption and reduction on Cu(100) in acidic solution is studied by electrochemical methods, in situ electrochemical scanning tunneling microscopy (EC-STM), surface enhanced Raman spectroscopy (SERS), and density functional theory (DFT) calculations. Electrochemical results show that reduction of nitrate starts at -0.3 V vs Ag/AgCl and reaches maximum value at -0.58 V. Over the entire potential region interrogated adlayers composed of nitrate, nitrite, or other intermediates are observed by using in situ STM. From the open-circuit potential (OCP) to -0.22 V vs Ag|AgCl, the nitrate ion is dominant and forms a (2 x 2) adlattice on the Cu(100) surface while nitrate forms a dominantly c(2 x 2) structure from -0.25 to -0.36 V. The interconversion between the nitrate and nitrite adlattices is observed. DFT calculations indicate that both nitrate and nitrite are twofold coordinated to the Cu(100) surface.

Nitrate adsorption and reduction on Cu(100) in acidic solution.

Progress in corrosion science at atomic and nanometric scales

Investigating the chemical nature of the adsorbed intermediate species on well-defined Cu single crystal substrates is crucial in understanding many electrocatalytic reactions. Herein, we systemati...

Early Stages of Electrochemical Oxidation of Cu(111) and Polycrystalline Cu Surfaces Revealed by in Situ Raman Spectroscopy.

Sulfate adsorption on Cu(111) studied by in-situ IRRAS and STM: revealing the adsorption site and desorption behavior

As a prototypical example of a metal-electrolyte interface the adsorption of sulfate on well defined Cu(111) single crystal electrodes from a 5 mM H 2 SO 4 solution has been studied by means of in-situ electrochemical scanning tunneling microscopy (EC-STM) and infrared reflection absorption spectroscopy (IRAS). The EC-STM images show the formation of the well-known Moire-like structure upon adsorption of sulfate on the Cu(111) surface. While IR frequency data fail to provide information about the anion adsorption site high-resolution STM images taken under specific tunneling conditions also clearly reveal the C 2v symmetry and the twofold bridging coordination of the sulfate adsorption complex. Analysis of the IR intensities, however, does show that the sulfate adsorption starts at a potential noticeably lower (less anodic) than the potential of first Moire formation. In this potential region the adsorbed sulfate is very mobile on the surface and difficult to image by STM. Adsorption rate and sulfate coverage are strongly dependent on the electrode potential. The slow adsorption process leading to a well ordered Moire structure is compared to a fast adsorption process by applying potential steps. Under the latter conditions no or only barely ordered sulfate adlayers are observed with STM. As shown by the IR measurements, however, the saturation coverage is hardly affected by the adsorption rate.

In‐situ Characterization of Metal/Electrolyte Interfaces: Sulfate Adsorption on Cu(111)

Cyanide adlayers on Pt(111) in chloride containing electrolytes studied by in situ, ex situ IRAS and LEED

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Sulfate adsorption on Cu(111) studied by in-situ IRRAS and STM: revealing the adsorption site and desorption behavior

In‐situ Characterization of Metal/Electrolyte Interfaces: Sulfate Adsorption on Cu(111)

Cyanide adlayers on Pt(111) in chloride containing electrolytes studied by in situ, ex situ IRAS and LEED