Spectroscopy adsorbed layer

Studies to determine the nature of intermediate species have been made on a variety of transition metals, and especially on Pt, with emphasis on the Pt(lll) surface. Techniques such as TPD (temperature-programmed desorption), SIMS, NEXAFS (see Table VIII-1) and RAIRS (reflection absorption infrared spectroscopy) have been used, as well as all kinds of isotopic labeling (see Refs. 286 and 289). On Pt(III) the surface is covered with C2H3, ethylidyne, tightly bound to a three-fold hollow site, see Fig. XVIII-25, and Ref. 290. A current mechanism is that of the figure, in which ethylidyne acts as a kind of surface catalyst, allowing surface H atoms to add to a second, perhaps physically adsorbed layer of ethylene this is, in effect, a kind of Eley-Rideal mechanism. 

Heiland W and Taglauer E 1975 Low energy ion scattering and Auger electron spectroscopy studies of clean nickel surfaces and adsorbed layers Surf. Sc/. 47 234-43... 

Examination of Adsorbed Layers by Thermal Desorption Mass Spectroscopy... 

PVA and TaM -for the 88%-hydrolyzed PVA. The same dependence was found for the adsorbed layer thickness measured by viscosity and photon correlation spectroscopy. Extension of the adsorption isotherms to higher concentrations gave a second rise in surface concentration, which was attributed to multilayer adsorption and incipient phase separation at the interface. The latex particle size had no effect on the adsorption density however, the thickness of the adsorbed layer increased with increasing particle size, which was attributed to changes in the configuration of the adsorbed polymer molecules. The electrolyte stability of the bare and PVA-covered particles showed that the bare particles coagulated in the primary minimum and the PVA-covered particles flocculated in the secondary minimum and the larger particles were less stable than the smaller particles. 

Effect of PVA Molecular Weight on Adsorbed Layer Thickness. Figure 4 shows the variation of reduced viscosity with volume fraction for the bare and PVA-covered 190nm-size PS latex particles. For the bare particles, nre(j/ is independent of and the value of the Einstein coefficient is ca. 3.0. For the covered particles, rired/ t increases linearly with tp. Table IV gives the adsorbed layer thicknesses calculated from the differences in the intercepts for the bare and covered particles and determined by photon correlation spectroscopy, as well as the root-mean-square radii of gyration of the free polymer coil in solution. The agreement of the adsorbed layer thicknesses determined by two independent methods is remarkable. The increase in adsorbed layer thickness follows the same dependence on molecular weight as the adsorption density, i.e., for the fully hydrolyzed PVA s and... 

The adsorbed layer thickness for the llOOnm-size particles could not be measured by photon correlation spectroscopy because of the lOOOnm upper limit of this instrument. Again, the agreement between the two methods is excellent. It is interesting that the adsorbed layer thickness increases with increasing latex particle size and that these values vary with the 0.5 power of the particle radius, i.e., where R is the particle radius. This re-... 

Several experimental parameters have been used to describe the conformation of a polymer adsorbed at the solid-solution interface these include the thickness of the adsorbed layer (photon correlation spectroscopy(J ) (p.c.s.), small angle neutron scattering (2) (s.a.n.s.), ellipsometry (3) and force-distance measurements between adsorbed layers (A), and the surface bound fraction (e.s.r. (5), n.m.r. ( 6), calorimetry (7) and i.r. (8)). However, it is very difficult to describe the adsorbed layer with a single parameter and ideally the segment density profile of the adsorbed chain is required. Recently s.a.n.s. (9) has been used to obtain segment density profiles for polyethylene oxide (PEO) and partially hydrolysed polyvinyl alcohol adsorbed on polystyrene latex. For PEO, two types of system were examined one where the chains were terminally-anchored and the other where the polymer was physically adsorbed from solution. The profiles for these two... 

Apart from the above techniques, the electromodulated reflectance spectroscopy combined with cyclic voltammetry has been utilized by Gaigalas et al. [14] in the investigations of electron transfer between the 2Fe-2S protein putidaredoxin and either bare or bekanamycin-modified Ag electrode. Of the two models considered, the free diffusion model, as compared to the adsorbed layer model, exhibited better concordance with the experimental data. After modification of the Ag electrode with bekanamycin, it exhibited only a small increase in the observed redox reaction... 

The vibrational spectrum of a molecule adsorbed on a metal surface contains detailed information about the metal-adsorbate bonds, the local orientation of the molecule, and intermolecular interactions within the adsorbate layer. It is this detailed information about the adsorbate layer that makes vibrational spectroscopy and most prominently IR spectroscopy an important tool in heterogeneous catalysis research. 

Morrissey 53) used transmission infrared spectroscopy to study protein adsorption onto silica particles in a heavy water (DzO) buffer. By observing the shift in the amide I absorption band, he could deduce the fraction of protein carbonyl groups involved in bonding to the silica surface. He found that bovine IgG had a bound fraction of 0.20 at low bulk solution concentrations, but only about 0.02 at high solution concentrations. However, neither prothrombin nor bovine serum albumin exhibited a change in bound fraction with concentration. Parallel experiments with flat silica plates using ellipsometry showed that the IgG-adsorbed layers had an optical thickness of 140 A and a surface concentration of 1.7 mg/m2 at low bulk solution concentration — in concentrated solutions the surface amount was 3.4 mg/m2 with a thickness of 320 A (Fig. 17). 

Abstract—Inelastic electron tunneling spectroscopy is used to investigate the adsorption of dimethyl-dimethoxysilane, dimethyldiethoxysilane, and dimethylvinylethoxy silane on alumina at the mono-layer level. Data obtained indicate that different adsorbed layers are produced when the silanes are introduced onto the oxide surface from solution or as a vapor. Silanes introduced in the same way onto different types of oxides suggest that alumina morphology also affects the adsorbed configuration. 

Concerning the experimental side of polymer adsorption studies the quantity A was only measurable at the early stage of the study, but in 19SS the thickness of the adsorbed layer became accessible to measurement by a hydrodynamic method and in 1961 the quantity p was first determined by infrared spectroscopy. Ellipsometry came up in 1963, which enabled both the adsorbance and the thickness of the adsorbed layer to be measured simultaneously. 

In ultraviolet photoelectron spectroscopy (UPS or U-PES), the irradiation (usually a He(I) (21.2 eV) or He(II) (40.8 eV) source) causes the displacement of a valence electron. Although an important method of studying the electronic nature of molecules in the gas phase, it is less useful for studying the surfaces of metals, since the valence electrons are in a continuous (conducting) energy band with a spread of about 10 eV. Adsorbed layers can, however, usefully be investigated in terms of the difference between the spectrum following adsorption and that for the clean metal surface. 

Here we discuss the application of low energy photoelectron transmission spectroscopy (LEPS) as a means for investigating the electronic properties of OOTF. In a typical experiment photoelectrons are ejected from the conductive substrate and after being transmitted through the adsorbed layer, the energy (and or angle) dependent electrons flux is measured as a function of incident photon energy, molecular film thickness, adsorbate and substrate types and temperature. 

Comparable experiments were performed with DexP-coated macroporous polystyrene-divinylbenzene (PS-DVB) particles [264] and with DexP, labelled with 4-amino-TEMPO, using EPR spectroscopy to study the conformation of the polymer chains [265]. Low substituted DexP gave thicker layers with lower density than highly substituted derivatives due to the presence of more loops and tails. With increasing DS of DexP, the stiffness of the adsorbed layers and, therefore, the density increases and the non-specific interaction of BSA with the DexP-coated PS-DVB surfaces seems to be restricted to the top of the adsorbed layer. 

Mucci A. and Morse J.W. (1985) Auger spectroscopy determination of the surface-most adsorbed layer composition on aragonite, calcite, dolomite, and magnesite in synthetic seawater. Amer. J. Sci. 285, 306-317. 

Immersion of the stepped Pt(s) [6(111) x (111)] surface into aqueous Br solutions [30] and subsequent examination of the surface by Auger spectroscopy and LEED revealed that Br has no particular affinity for surface steps. Instead, the differences in adsorption behavior of the stepped and smooth (111) surfaces are due to the fact that different long-range adsorbed layer... 

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