Metal surfaces spectroscopic studies

Bradley, J.S. et al., Surface spectroscopic study of the stabilization mechanism for shape-selectively synthesized nanostructured transition metal colloids, J. Am. Chem. Soc., 122, 4631, 2000. 

Most of the contemporary research areas that utilize surface chemistry techniques employ thin organic films that have been physically or chemically adsorbed onto a solid (usually metallic) substrate. The use of conducting metal surfaces is due not only to their relevance to many different fields, but also to the fact that many surface spectroscopic techniques (Table I) need such a surface in order to produce high-quality spectra. This criterion effectively eliminated many interesting non-metallic surfaces from study using modem surface-sensitive spectroscopic methods. 

In situ methods permit the examination of the surface in its electrolytic environment with application of the electrode potential of choice. Usually they are favored for the study of surface layers. Spectroscopic methods working in the ultra high vacuum (UHV) are a valuable alternative. Their detailed information about the chemical composition of surface films makes them an almost inevitable tool for electrochemical research and corrosion studies. Methods like X-ray Photoelectron Spectroscopy (XPS), UV Photoelectron Spectroscopy (UPS), Auger Electron Spectroscopy (AES) and the Ion Spectroscopies as Ion Scattering Spectroscopy (ISS) and Rutherford Backscattering (RBS) have been applied to metal surfaces to study corrosion and passivity. 

Overall, the metalloid aluminium and gallium clusters bear some relationship to fragments of the bulk metals, protected and stabilised by the ligands on the surface, and as such can be considered intermediate between molecules and metals. They show a marked sensitivity to preparative conditions and the steric influence of the ligands on the surface. Spectroscopic studies and theoretical calculations on the clusters are not discussed here but are summarised in recent review articles, and these additional studies provide a... 

B.E. Bent. Bonding and Reactivity of Unsaturated Hydrocarbons on Transition Metal Surfaces Spectroscopic and Kinetic Studies of Platinum and Rhodium Single Crystal Surfaces. PhD thesis. University of California, Berkeley, 1986. 

If a surface, typically a metal surface, is irradiated with a probe beam of photons, electrons, or ions (usually positive ions), one generally finds that photons, electrons, and ions are produced in various combinations. A particular method consists of using a particular type of probe beam and detecting a particular type of produced species. The method becomes a spectroscopic one if the intensity or efficiency of the phenomenon is studied as a function of the energy of the produced species at constant probe beam energy, or vice versa. Quite a few combinations are possible, as is evident from the listing in Table VIII-1, and only a few are considered here. 

Goodman D W 1996 Chemical and spectroscopic studies of metal oxide surfaces J. Vac. Sc/. Technol. A 14 1526... 

Iron is the most abundant, useful, and important of all metals. For example, in the 70-kg human, there is approximately 4.2 g of iron. It can exist in the 0, I, II, III, and IV oxidation states, although the II and III ions are most common. Numerous complexes of the ferrous and ferric states are available. The Fe(II) and Fe(III) aquo complexes have vastly different pAa values of 9.5 and 2.2, respectively. Iron is found predominantly as Fe (92%) with smaller abundances of Fe (6%), Fe (2.2%), and Fe (0.3%). Fe is highly useful for spectroscopic studies because it has a nuclear spin of. There has been speculation that life originated at the surface of iron-sulfide precipitants such as pyrite or greigite that could have caused autocatalytic reactions leading to the first metabolic pathways (2, 3). 

Secondary Ion Mass Spectroscopic Studies of Adsorption and Reaction at Metal Surfaces Correlations with Other Surface-Sensitive Techniques... 

Vibrational spectroscopic studies of heterogeneously catalyzed reactions refer to experiments with low area metals in ultra high vacuum (UHV) as well as experiments with high area, supported metal oxides over wide ranges of pressure, temperature and composition [1]. There is clearly a need for this experimental diversity. UHV studies lead to a better understanding of the fundamental structure and chemistry of the surface-adsorbate system. Supported metals and metal oxides are utilized in a variety of reactions. Their study leads to a better understanding of the chemistry, kinetics and mechanisms in the reaction. Unfortunately, the most widely used technique for determining adsorbate molecular structure in UHV,... 

There are relatively few examples of C-C bond formation on solid surfaces under UHV conditions. There are virtually no examples of catalytic C-C bond formation under such conditions. Perhaps the closest precedent for the present studies on reduced Ti02 can be found in the studies of Lambert et al. on single crystal Pd surfaces. Early UHV studies demonstrated that acetylene could be trimerized to benzene on the Pd(lll) surface in both TPD and modulated molecular beam experiments [9,10]. Subsequent studies by the same group and others [11,12] demonstrated that this reaction could be catalyzed at atmospheric pressure both by palladium single crystals and supported palladium catalysts. While it is not clear that catalysis was achieved in UHV, these and subsequent studies have provided valuable insights into the mechanism of this reaction as catalyzed by metals, including spectroscopic evidence for the hypothesized metallacyclopentadiene intermediates [10,13,14]. 

Westermark, G. and Persson, 1. (1998) Chemisorption of tertiary phosphines on coinage and platinum group metal powders. An infrared reflectance absorption spectroscopic, enhanced Raman spectroscopic and surface coverage study. Colloids and Surfaces A -Physicochemical and Engineering Aspects, 144, 149-166. 

Recent work by Stipp and Hochella (1991) provide evidence for the processes of reconfiguration and hydration at the calcite surface. These results may provide a basis for future spectroscopic studies of trace metal adsorption and subsequent solid-solution formation. 

In addition to the indirect experimental evidence coming from work function measurements, information about water orientation at metal surfaces is beginning to emerge from recent applications of a number of in situ vibrational spectroscopic techniques. Infrared reflection-absorption spectroscopy, surface-enhanced Raman scattering, and second harmonic generation have been used to investigate the structure of water at different metal surfaces, but the pictures emerging from all these studies are not always consistent, partially because of surface modification and chemical adsorption, which complicate the analysis. 

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