Adsorption metal oxide surfaces

Effect of Precontamination on PLL(375)-g[5.6]-PEG-(5) Adsorption. Metal oxide surfaces that exhibited large amounts of hydrocarbon surface contamination nevertheless adsorbed a layer of PLL(375)-g[5.6]-PEG(5) that suppressed subsequent serum adsorption. Titanium dioxide waveguides that were not cleaned according to the procedure described in section 1.4.1 exhibited substantial hydrocarbon surface contamination (see Tables 2 and 3 and Figure 2). However, these XPS data also indicate that an additional layer of PLL(375)-g[5.6]-PEG-(5) does, indeed, adsorb onto this contaminated surface. Furthermore, OWLS experiments showed that the typical adsorbed areal density of 120 ng/cm forms on contaminated titanium dioxide waveguides and that this adsorbed layer of polymer suppresses subsequent serum protein adsorption by about 95%. That is, the adsorption and performance characteristics of PLL(375)-g[5.6]-PEG(5) are identical in the case of both contaminated and cleaned titanium dioxide surfaces. 

It is unlikely in real tribological events that adsorbed mono-layers work solely to provide lubrication. Instead, adsorption and chemical reactions may occur simultaneously in most cases of boundary lubrication. For example, fatty acid is usually regarded as a friction modiher due to good adsorp-tivity, meanwhile its molecules can react with metal or a metal oxide surface to form metallic soap which provides protection to the surface at the temperature that is higher than its own melting point. 

A highly detailed picture of a reaction mechanism evolves in-situ studies. It is now known that the adsorption of molecules from the gas phase can seriously influence the reactivity of adsorbed species at oxide surfaces[24]. In-situ observation of adsorbed molecules on metal-oxide surfaces is a crucial issue in molecular-scale understanding of catalysis. The transport of adsorbed species often controls the rate of surface reactions. In practice the inherent compositional and structural inhomogeneity of oxide surfaces makes the problem of identifying the essential issues for their catalytic performance extremely difficult. In order to reduce the level of complexity, a common approach is to study model catalysts such as single crystal oxide surfaces and epitaxial oxide flat surfaces. 

It was shown in a number of works [29] that impurity conductivity of thin zinc oxide films are extremely sensitive to adsorption of atoms of various metals (see Chapters 2 and 3). Using this feature of oxide films, we first employed the sensor method to study evaporation of superstechiometric atoms of metals from metal oxide surfaces, zinc oxide in particular [30]. 

When a metal oxide surface is exposed to water, adsorption of water molecules takes place as shown in Equation 2.1. Cation sites can be considered as Lewis acids and interact with donor molecules like water through a combination of ion-dipole attraction and orbital overlap. Subsequent protonation and deprotonation of the surface hydroxyls produce charged oxide surfaces as shown in Equation 2.2 and Equation 2.3, respectively ... 

At low pH, where resorption reactions are minimal, the photodissolution process may be represented as a two-step process involving adsorption of ligand L to metal oxide surface sites followed by detachment of reduced metal ions that is, for an iron oxyhydroxide ... 

Adsorption of Organic Reductants and Subsequent Electron Transfer on Metal Oxide Surfaces... 

The most direct evidence for surface precursor complex formation prior to electron transfer comes from a study of photoreduc-tive dissolution of iron oxide particles by citrate (37). Citrate adsorbs to iron oxide surface sites under dark conditions, but reduces surface sites at an appreciable rate only under illumination. Thus, citrate surface coverage can be measured in the dark, then correlated with rates of reductive dissolution under illumination. Results show that initial dissolution rates are directly related to the amount of surface bound citrate (37). Adsorption of calcium and phosphate has been found to inhibit reductive dissolution of manganese oxide by hydroquinone (33). The most likely explanation is that adsorbed calcium or phosphate molecules block inner-sphere complex formation between metal oxide surface sites and hydroquinone. 

Mn(II) adsorption on metal oxide surfaces. The binding of Mn(II) on y-FeOOH can be understood in a surface coordination chemical framework. The surface groups on a metal oxide are amphoteric and the hydrolysis reactions can be written ... 

CO adsorption, 28 8 metal-alkene surfaces, 29 85-86 metal oxide surfaces, 29 55-92 oxide surface, 28 26 solid surfaces, 29 55-92 surface chemistry, 29 55-92 yield, chemisorbed layer, 29 59-62 factors affecting yield, 29 61 Photoemission... 

When an ionic/nonionic surfactant mixture adsorbs on a metal oxide surface, the admicelle exhibits negative deviation from ideality (74). This means that the adsorption level is higher than it would be if the admicelle were ideal, at a specific surfactant concentration below the CMC. Above the CMC, the adsorption level is dictated by the relative enhancement of micelle formation vs. admicelle formation. In this region, the level of adsorption can be viewed as the result of the competition between micelles and admicelles for surfactant. In analogy, the surface tension above the CMC can be viewed as competition between the monolayer and micelles for surfactant. 

The adsorption of surfactant mixtures on metal oxide surfaces (e.g., minerals) from aqueous solutions is an important process in such applications as enhanced oil recovery and detergency. Since surfactants used in real-world applications are almost always mixtures,... 

Grazing incidence EXAFS spectroscopic studies of Pb(II)aq adsorption on metal oxide surfaces - effect of differences in surface functional groups on reactivity... 

Thus, the possibility of adsorption is of primary importance. Adsorption may originate either from chelating properties of the organic substrate toward surface metal species or, because of the low hydrophobicity of the metal oxide surface, from the expulsion of the organic molecules from the solution for entropy reasons. Because there is depletion of substrate at the catalyst surface when degradation takes place, migration from the solution is assisted by a concentration difference in the two environments. 

Electrocatalyzed oxygen reduction proceeds always in the adsorbed state. Figure 17 depicts the three different modes of oxygen adsorption on a metal or metal oxide surfaces, which are supposed to be of relevance for cathodic oxygen reduction (113). So-called Griffith adsorption (I), which has been observed by Gland and co-workers (114) on Pt(l 11) surfaces due to interac-... 

Large adsorbates, such as bi-isonicotinic acid, may bind to a surface at several sites which are sufficiently far apart not to interact strongly in a direct way. This kind of system is by necessity large and complex, and few detailed studies have been reported on such systems. Various structural aspects of bi-isonicotinic acid adsorption on rutile and anatase TiC>2 surfaces have been presented in several recent studies [68, 77, 78]. Bi-isonicotinic acid adsorption on TiC>2 surfaces is not only taken as a problem of direct interest to the photoelectrochemical applications, but also serves as a model system for surface science investigations of phenomena connected to the adsorption of large organic adsorbates on metal oxide surfaces. 

Since gas phase ionization potentials indicate that secondary alcohols should be more easily oxidized than primary alcohols, the relative reactivity cannot be governed by thermodynamic factors associated with primary electron exchange. A logical explanation for the ordering of the reactivity may relate to the preferential adsorption of the primary alcohol on the metal oxide surface. 

McBride and Wesselink (1988) studied IR spectra of catechol adsorbed onto the oxide surface and found evidence that the compound was chemically altered, indicating that chemisorption was the dominant mechanism. In addition to catechols, phenols are known to adsorb onto metal oxide surfaces. This adsorption is dependent on the number and position of hydroxy substitutions on the benzene ring. Diphenolic compounds adsorb to a greater extent than monophenolic compounds, suggesting the formation of a bidentate bond with the metal oxide. This bidentate bond is formed when the two phenolic ligands coordinate with one or two surface metal ions (McBride and Wesselink, 1988). 

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