Electron loss spectroscopy, surface structure

Over the past 10 years a multitude of new techniques has been developed to permit characterization of catalyst surfaces on the atomic scale. Low-energy electron diffraction (LEED) can determine the atomic surface structure of the topmost layer of the clean catalyst or of the adsorbed intermediate (7). Auger electron spectroscopy (2) (AES) and other electron spectroscopy techniques (X-ray photoelectron, ultraviolet photoelectron, electron loss spectroscopies, etc.) can be used to determine the chemical composition of the surface with the sensitivity of 1% of a monolayer (approximately 1013 atoms/cm2). In addition to qualitative and quantitative chemical analysis of the surface layer, electron spectroscopy can also be utilized to determine the valency of surface atoms and the nature of the surface chemical bond. These are static techniques, but by using a suitable apparatus, which will be described later, one can monitor the atomic structure and composition during catalytic reactions at low pressures (< 10-4 Torr). As a result, we can determine reaction rates and product distributions in catalytic surface reactions as a function of surface structure and surface chemical composition. These relations permit the exploration of the mechanistic details of catalysis on the molecular level to optimize catalyst preparation and to build new catalyst systems by employing the knowledge gained. 

Employing TERS in UHV systems There are a number of surface science tools available for samples in UHV which allow us to characterize the state of a surface. Surface and adlayer structures can be determined by LEED (low electron energy diffraction) as weU as by SPM (scanning probe microscopy) techniques. While the kind of chemical interactions can be studied, for example, with AES (Auger electron spectroscopy), EELS (energy electron loss spectroscopy) permits the identification of the chemical nature of the adsorbed species. TERS, on the other hand, may provide similar but also complementary information on the chemical identity under UHV conditions. As an additional advantage, TERS and SPM permit the identification and characterization of the spatial region from which this information is accumulated. 

Several techniques that provide information about composition and structure on the molecular level were discussed. For instance, secondary ion mass spectroscopy (SIMS), XPS which provide information about surface composition and the chemical environment and bonding of surface species, and ultraviolet photoelectron spectroscopy (UPS), which probes the density of electronic states in the valence band of materials. Also, the low energy electron diffraction (LEED) and high resolution energy electron loss spectroscopy (HREELS) are electronscattering techniques that are uniquely suited to yield the structure of the surface... 

How then, can one recover some quantity that scales with the local charge on the metal atoms if their valence electrons are inherently delocalized Beyond the asymmetric lineshape of the metal 2p3/2 peak, there is also a distinct satellite structure seen in the spectra for CoP and elemental Co. From reflection electron energy loss spectroscopy (REELS), we have determined that this satellite structure originates from plasmon loss events (instead of a two-core-hole final state effect as previously thought [67,68]) in which exiting photoelectrons lose some of their energy to valence electrons of atoms near the surface of the solid [58]. The intensity of these satellite peaks (relative to the main peak) is weaker in CoP than in elemental Co. This implies that the Co atoms have fewer valence electrons in CoP than in elemental Co, that is, they are definitely cationic, notwithstanding the lack of a BE shift. For the other compounds in the MP (M = Cr, Mn, Fe) series, the satellite structure is probably too weak to be observed, but solid solutions Coi -xMxl> and CoAs i yPv do show this feature (vide infra) [60,61]. 

Figure 8.14 High-resolution electron energy loss spectroscopy (HREELS) and low-energy electron diffraction of CO adsorbed on a Rh(l 11) surface, along with structure models. The HREELS spectra show the C-O and metal-CO stretch vibrations of linear and threefold CO on rhodium (from R.Linke etal. [56]).

In order to elucidate the results of the CO TPD experiment, the detailed structure of the oxygen-modified Mo(l 12) surfaces and the adsorption sites of CO on these surfaces have been considered. Zaera et al. (14) investigated the CO adsorption on the Mo(l 10) surface by high-resolution electron-energy-loss spectroscopy (HREELS) and found vatop sites. Francy et al. (75) also found a 2100 cm loss for CO on W(IOO) and assigned it to atop CO. Recently, He et al. (16) indicated by infrared reflection-absorption spectroscopy that at low exposures CO is likely bound to the substrate with the C-0 axis tilted with respect to the surface normal. They, however, have also shown that CO molecules adsorbed on O-modified Mo(l 10) exhibi Vc-o 2062 and 1983 cm L characteristic to CO adsorbed on atop sites. Thus it is supposed that CO adsorbs on top of the first layer Mo atoms. 

Techniques of electron spectroscopies have emerged to become the principal means for investigating electronic structures of solids and surfaces (Rao, 1985 Mason et al, 1986). Most of these techniques involve the analysis of the kinetic energy of the ejected or scattered electrons. Some of the important techniques of electron spectroscopy used to study solids are photoelectron spectroscopy using X-rays (XPS) or UV radiation (UVPS), Auger electron spectroscopy (AES) and electron energy loss spectroscopy, (EELS). All these techniques are surface-sensitive and probe 25 A or less of solids. Cleanliness of the surfaces and ultra-high vacuum ( 10 — 10 " torr) are there-... 

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