Solid surfaces, chemical structure

A schematic diagram of a vacuum system for liquid-solid surface chemical and electrochemical studies, including structural investigations, is shown in Fig. 1. The sample surface under investigation is shuttled back and forth between UHV and various solutions at ambient pressure without... 

First, a complete description of the adsorbent is required this must include details of its solid structure, surface chemical structure, pore size and shape. One starts by assuming that the pores in the model adsorbent are all of the same size and shape and that they are unconnected. Secondly, the nature of the fluid-fluid and fluid-solid interactions must be precisely defined since the validity of the calculations is dependent on the accuracy of the intermolecular potential functions. 

The electronic structures of porous solids have been examined by X-ray photoelectron spectroscopy (XPS). However, the penetration depth of electrons is 1 nm at best and XPS cannot examine electronic structures of inner pore-walls. XPS has been often used for the determination of surface chemical structures such as surface functional groups in activated carbon. Ar etching leads to the depth profile of electronic structures. This depth profile is often effective to evidence the presence of nanoporosity. 

Taking advantage of the intrinsic physical and chemical differences of surfaces introduced by the discontinuity of the bulk enviromuent. Specifically, most solids display specific structural relaxations and reconstructions, surface... 

In general there are two factors capable of bringing about the reduction in chemical potential of the adsorbate, which is responsible for capillary condensation the proximity of the solid surface on the one hand (adsorption effect) and the curvature of the liquid meniscus on the other (Kelvin effect). From considerations advanced in Chapter 1 the adsorption effect should be limited to a distance of a few molecular diameters from the surface of the solid. Only at distances in excess of this would the film acquire the completely liquid-like properties which would enable its angle of contact with the bulk liquid to become zero thinner films would differ in structure from the bulk liquid and should therefore display a finite angle of contact with it. 

Sputtered Neutral Mass Spectrometry (SNMS) is the mass spectrometric analysis of sputtered atoms ejected from a solid surface by energetic ion bombardment. The sputtered atoms are ionized for mass spectrometric analysis by a mechanism separate from the sputtering atomization. As such, SNMS is complementary to Secondary Ion Mass Spectrometry (SIMS), which is the mass spectrometric analysis of sputtered ions, as distinct from sputtered atoms. The forte of SNMS analysis, compared to SIMS, is the accurate measurement of concentration depth profiles through chemically complex thin-film structures, including interfaces, with excellent depth resolution and to trace concentration levels. Genetically both SALI and GDMS are specific examples of SNMS. In this article we concentrate on post ionization only by electron impact. 

EXAFS is a nondestructive, element-specific spectroscopic technique with application to all elements from lithium to uranium. It is employed as a direct probe of the atomic environment of an X-ray absorbing element and provides chemical bonding information. Although EXAFS is primarily used to determine the local structure of bulk solids (e.g., crystalline and amorphous materials), solid surfaces, and interfaces, its use is not limited to the solid state. As a structural tool, EXAFS complements the familiar X-ray diffraction technique, which is applicable only to crystalline solids. EXAFS provides an atomic-scale perspective about the X-ray absorbing element in terms of the numbers, types, and interatomic distances of neighboring atoms. 

A large number of possible applications of arrays of nanoparticles on solid surfaces is reviewed in Refs. [23,24]. They include, for example, development of new (elect-ro)catalytical systems for applications as chemical sensors, biosensors or (bio)fuel cells, preparation of optical biosensors exploiting localized plasmonic effect or surface enhanced Raman scattering, development of single electron devices and electroluminescent structures and many other applications. 

Muller (1951, 1956) developed this instrument, which for the first time enabled extensive details of the atomic structure of a solid surface to be seen directly. Figure 1.1 illustrates schematically the basic construction of a FIM. The specimen is prepared in the form of a fine wire or needle, which has been chemically or electrochemically polished to a sharp point with an end radius typically 50-100 nm. It is mounted along the axis of a vacuum chamber, about 50 mm from a phosphor screen (perhaps 75 mm in diameter). The specimen is mounted on an electrical insulator within a cryostat, and it can be raised to a high positive potential (3-30 kV) by means of the leads attached. 

Adsorption is a physicochemical process whereby ionic and nonionic solutes become concentrated from solution at solid-liquid interfaces.3132 Adsorption and desorption are caused by interactions between and among molecules in solution and those in the structure of solid surfaces. Adsorption is a major mechanism affecting the mobility of heavy metals and toxic organic substances and is thus a major consideration when assessing transport. Because adsorption is usually fully or partly reversible (desorption), only rarely can it be considered a detoxification process for fate-assessment purposes. Although adsorption does not directly affect the toxicity of a substance, the substance may be rendered nontoxic by concurrent transformation processes such as hydrolysis and biodegradation. Many chemical and physical properties of both aqueous and solid phases affect adsorption, and the physical chemistry of the process itself is complex. For example, adsorption of one ion may result in desorption of another ion (known as ion exchange). 

Adsorption is the preferential concentration of a species at the interface between two phases. Adsorption on solid surfaces is a very complex process and one that is not well understood. The surfaces of most heterogeneous catalysts are not uniform. Variations in energy, crystal structure, and chemical composition will occur as one moves about on the catalyst surface. In spite of this it is generally possible to divide all adsorption phenomena involving solid surfaces into two main classes physical adsorption and chemical adsorption (or chemisorption). Physical adsorption arises from intermolecular forces... 

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