Role of surface structure

Markovic NM, Tidswell IM, Ross PN. 1994. Oxygen and hydrogen peroxide reduction on the gold(lOO) surface in alkaline electrolyte the roles of surface structure and hydroxide adsorption. Langmuir 10 1-4. 

Both the data on hydrogen adsorption and formic acid oxidation show pronounced structural sensitivity, thus confirming a paramount role of surface structure in electrocatalytic reactions. It can be concluded that each crystallographic orientation represents a distinct electrochemical (chemical) entity. The investigation of stepped surfaces seems to be necessary to reach an understanding of these systems on a molecular level. Hydrogen adsorption shows dependences on the terrace orientation, step orientation, and step density. All the... 

Since most of the papers in this symposium deal primarily with the role of surface composition in industrial applications, in this section we depart from that path to consider an example of the role of surface structure in the performance microelectronics devices. 

The frictional behavior we are concerned with is a consequence of rubbing contact and involves the interaction of surfaces. Real surfaces are neither geometrically nor molecularly smooth. Discussion of the complexities of contact theory and their influence on rubbing behavior is the subject of Chapter 12. But even a simple treatment of the basic theory of friction involves the role of surface structure. 

Rakovan J, Reeder RJ (1994) Differential incorporation of trace elements and dissymmetrization in apatite The role of surface structure during growth. Am Mineral 79 892-903 Rakovan J, Reeder RJ (1996) Intraciystalline rare earth element distributions in apatite ... 

Surfaces can be active in inducing blood clotting, and there is much current searching for thromboresistant synthetic materials for use in surgical repair of blood vessels (see Ref. 111). It may be important that a protective protein film be strongly adsorbed [112]. The role of water structure in cell-wall interactions may be quite important as well [113]. 

Very recently, considerable effort has been devoted to the simulation of the oscillatory behavior which has been observed experimentally in various surface reactions. So far, the most studied reaction is the catalytic oxidation of carbon monoxide, where it is well known that oscillations are coupled to reversible reconstructions of the surface via structure-sensitive sticking coefficients of the reactants. A careful evaluation of the simulation results is necessary in order to ensure that oscillations remain in the thermodynamic limit. The roles of surface diffusion of the reactants versus direct adsorption from the gas phase, at the onset of selforganization and synchronized behavior, is a topic which merits further investigation. 

The structure of water at the PVA/quartz interface was investigated by SFG spectroscopy. Two broad peaks were observed in the OH-stretching region at 3200 and 3400 cm , due to ice-like and liquid-like water, respectively, in both cases. The relative intensity of the SFG signal due to liquid-like water increased when the PVA gel was pressed against the quartz surface. No such increase of the liquid-like water was observed when the PVA gel was contacted to the hydro-phobic OTS-modified quartz surface where friction was high. These results suggest the important role of water structure for low friction at the polymer gel/solid interfaces. 

J. W. Linnett. There were 11 papers with theoretical inputs but with more emphasis given to new developments in experimental methods including structural (LEED and electron microscopy) and surface spectroscopies. LEED provided crucial evidence for the role of surface steps at platinum single crystals in the dissociation of various diatomic molecules, while electron microscopy revealed the role of dislocations as sites of high reactivity of... 

Fig. 10). With the completion of the structure transition, the current should drop to zero, which is indeed the case except for peak B, where a slight leak current is seen (ascribed to the side reaction Cu++ I c > Cu+). According to the theory by Bewick, Fleischmann and Thirsk (BFT) the transients can be used to distinguish between instantaneous and progressive nucleation [45], A corresponding analysis revealed that the falling part of the transients agrees well with the model for instantaneous nucleation, while the rising part shows a systematic deviation. This was explained by the existence of surface defects on a real electrode in contrast to the ideal case of a defect-free surface assumed in the theoretical model. By including an adsorption term in the BFT theory to account for Cu deposition at defects, the experimentally obtained transients could indeed be reproduced very well [44], We shall return to the important role of surface defects in metal deposition later (sec. 3.2).

The structure and dynamics of clean metal surfaces are also of importance for understanding surface reactivity. For example, it is widely held that reactions at steps and defects play major roles in catalytic activity. Unfortunately a lack of periodicity in these configurations makes calculations of energetics and structure difficult. When there are many possible structures, or if one is interested in dynamics, first-principle electronic structure calculations are often too time consuming to be practical. The embedded-atom method (EAM) discussed above has made realistic empirical calculations possible, and so estimates of surface structures can now be routinely made. 

Surfactant adsorption on solids from aqueous solutions plays a major role in a number of interfacial processes such as enhanced oil recovery, flotation and detergency. The adsorption mechanism in these cases is dependent upon the properties of the solid, solvent as well as the surfactant. While considerable information is available on the effect of solid properties such as surface charge and solubility, solvent properties such as pH and ionic strength (1,2,3), the role of possible structural variations of the surfactant in determining adsorption is not yet fully understood. 

Mankind has used some form of cement for thousands of years to build houses and monuments. Some examples are the pyramids (3000 BC) and the Colosseum (2000 BC), indicating an early awareness of the role of surface and colloidal chemistry. In modern times, besides small structures such as houses, the use of cement has been widened to include very large constructions such as dams. The main aim of using cement is to bind two bricks with a material consisting of very fine particles, and which hardens after water has evaporated. 

In the past decades, it has become more and more obvious that students and scientists of chemistry and engineering should have some understanding of surface and colloid chemistry. The textbooks on physical chemistry tend to introduce this subject insufficiently. Modern nanotechnology is another area where the role of surface and chemistry is found of much importance. Medical diagnostics applications are also extensive, where both microscale and surface reactions are determined by different aspects of surface and colloid chemical principles. Drug delivery is much based on lipid vesicles (self-assembly structure) that are stabilized by various surface forces. 

From a description of the geometric structure of electrified interfaces we moved to a description of models for electrochemical electron transfer across an electrode interface. The science of atomic scale electrochemistry was presented with an emphasis on the bonding of water molecules and anions on electrode surfaces. Subsequently, we presented an in-depth description of the role of surface bonding in a number of important electrocatalytic processes for energy conversion. We have attempted to illustrate how closely surface bonding and catalytic activity are related. 

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