Elemental surface structure

The major role of TOF-SARS and SARIS is as surface structure analysis teclmiques which are capable of probing the positions of all elements with an accuracy of <0.1 A. They are sensitive to short-range order, i.e. individual interatomic spacings that are <10 A. They provide a direct measure of the interatomic distances in the first and subsurface layers and a measure of surface periodicity in real space. One of its most important applications is the direct determination of hydrogen adsorption sites by recoiling spectrometry [12, 4T ]. Most other surface structure teclmiques do not detect hydrogen, with the possible exception of He atom scattering and vibrational spectroscopy. 

Carbon blacks are synthetic materials which essentially contain carbon as the main element. The structure of carbon black is similar to graphite (hexagonal rings of carbon forming large sheets), but its structure is tridimensional and less ordered. The layers of carbon blacks are parallel to each other but not arranged in order, usually forming concentric inner layers (turbostratic structure). Some typical properties are density 1.7-1.9 g/cm pH of water suspension 2-8 primary particle size 14-250 nm oil absorption 50-300 g/100 g specific surface area 7-560 m /g. 

Thermal transmittance (t/-value) defines the ability to an element of structure to transmit heat under steady-state conditions. It is a measure of the quantity of heat that will flow through unit area in unit time per unit difference in temperature of the individual environments between which the structure intervenes. It is calculated as the reciprocal of the sum of the resistance of each component part of the structure, including the resistance of any air space or cavity and of the inner and outer surfaces. It is expressed as W/m K. 

The physicochemical properties of carbon are highly dependent on its surface structure and chemical composition [66—68], The type and content of surface species, particle shape and size, pore-size distribution, BET surface area and pore-opening are of critical importance in the use of carbons as anode material. These properties have a major influence on (9IR, reversible capacity <2R, and the rate capability and safety of the battery. The surface chemical composition depends on the raw materials (carbon precursors), the production process, and the history of the carbon. Surface groups containing H, O, S, N, P, halogens, and other elements have been identified on carbon blacks [66, 67]. There is also ash on the surface of carbon and this typically contains Ca, Si, Fe, Al, and V. Ash and acidic oxides enhance the adsorption of the more polar compounds and electrolytes [66]. 

The continued development of new single-source molecular precursors should lead to increasingly complex mixed-element oxides with novel properties. Continued work with grafting methods will provide access to novel surface structures that may prove useful for catalytic apphcations. Use of molecular precursors for the generation of metal nanoparticles supported on various oxide supports is another area that shows promise. We expect that the thermolytic molecular precursor methods outlined here will contribute significantly to the development of new generations of advanced materials with tailored properties, and that it will continue to provide access to catalytic materials with improved performance. 

The latter report demonstrated the unique ability of this technique to resolve surface structure as well as surface composition at the electrified solid-liquid interfaces. In particular, STM has become an important tool for ex situ and in situ characterization of surfaces at the atomic level, in spite its significant limitations regarding surface composition characterization for bimetallic systems, such as the lack of contrast for different elements and the scanned surface area being too small to be representative for the entire surface. To avoid these limitations, STM has been mostly used as a complementary tool in surface characterization. 

Mono- or single-crystal materials are undoubtedly the most straightforward to handle conceptually, however, and we start our consideration of electrochemistry by examining some simple substances to show how the surface structure follows immediately from the bulk structure we will need this information in chapter 2, since modern single-crystal studies have shed considerable light on the mechanism of many prototypical electrochemical reactions. The great majority of electrode materials are either elemental metals or metal alloys, most of which have a face-centred or body-centred cubic structure, or one based on a hexagonal close-packed array of atoms. 

More importantly, it is vital to be certain that the surface structure is not the result of a reconstruction due to adsorption of any contaminant from the air. Similarly, elemental analysis is only meaningful when the elements determined come from the sample and not exposure to the atmosphere. 

In secondary ion mass spectrometry (SIMS), a primary ion beam bombards the surface and a mass spectrometer analyses the ions sputtered from the surface by the primary bombardment. This extremely sensitive technique provides both elemental and structural information. 

Elemental and Structural Characterization Many oxidation reactions occur on mixed oxides of complex composition, such as SbSn(Fe)0, VPO, FePO, heteropolycompounds, etc. Very often the active surfaces are not simple terminations of the three dimensional structure of the bulk phases. There is need to extensively apply structural characterization techniques to the study of catalysts, if possible in their working state. 

The study of the link between the surface structure of an electrode and its reactivity in electrode processes is considered as an important element of the investigations in modem electrochemistry. 

So far, the bonding and surface structure aspects of electrocatalysis have been presented in a somewhat abstract sort of way. In order to make electrocatalysis a little more real, it is helpful to go through an example—that of the catalysis of the evolution of oxygen from alkaline solutions onto substances called perovskites. Such materials are given by the general formula RT03, where R is a rare earth element such as lanthanum, and T is a transition metal such as nickel. In the electron catalysis studied, the lattice of the perovskite crystal was replicated with various transition metals, i.e., Ni, Co, Fe, Mn, and Cr, the R remaining always La. 

While low coordination number sites, steps, and kinks, are the active sites for bond breaking in platinum, the atomic terrace sites with larger coordination numbers may also become active sites with unique chemistry for other elements. It will perhaps become possible to identify the bond-breaking ability of various coordination number sites of a given metal in breaking H—H, C—H, C —C, 0=0, N=N, etc., chemical bonds. By varying the atomic surface structure, which would change the relative concentrations of the different coordination number surface sites, the product distribution in surface chemical reactions may be markedly varied. 

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