Metal crystals, electrode/solution interface

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Solid metal surfaces contain numerous defects such as atomic steps, point defects and dislocations and grain boundaries that ean influence double layer properties. Most basic experiments on the structure of the eleetric double layer are therefore carried out on liquid electrodes, mostly mercury. This also avoids problems related to rugosity and crystal orientation. Experiments with polycrystalline solids yield an average value for the double layer properties of the electrode-solution interface. 

The experimental data concerning capacitance of edl at the selected faces of Bi, Sb, and Cd single crystals in solutions of surface inactive electrolytes in water and organic solvent were analyzed in terms of various models [11]. From these data, it follows that the interface electrode/electrolyte properties depend hoth on the crystallographic and electronic characteristics of the metal and on the nature of the solvent. 

When using single-crystal electrodes, it is assumed that the structure of their surfaces reflects the structure of the bulk crystal. However, it appears that, frequently, the surface structure is different from that of the bulk due to their different atomic surroundings. In the bulk crystal, each metal atom is surrounded by identical atoms fixed within the well-defined structure. In contrast, the surface atoms participate in the interactions with metal atoms forming the crystal, and are involved as well in the interactions with the components of the solution at the solid/liquid interface. These asymmetrical interactions of the surface atoms may lead to the breakage of the old and formation of the new bonds, followed by the displacement of the surface atoms to the positions of the lower surface energy. The process of formation... 

Infrared spectroscopy is frequently applied to investigate CO adsorption on electrodes, because CO is important as an intermediate and surface poison in many electrocatalytic reactions and the C-O stretching vibrational modes of the adlayer are sensitive to the chemical environment at the metal/solution interface. Infrared spectra of CO adsorbed on low-index surface planes of Pt single-crystal electrodes have become a benchmark for use in understanding the behavior of CO on other surfaces. Related approaches have been extended to bulk single-crystal metal electrodes that include Pd [66, 67], Ir [68-71], Rh [13, 70], Ru [72-74], Ni [75, 76] and Au [77]. 

Abstract The adsorption of insoluble surfactants, spread as a monolayer at the gas-solution interface (GS), onto an electrified metal-solution (MS) interface of a gold single-crystal electrode has been investigated. 

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