Infrared spectroscopy surfaces

Chabal YJ (1988) Surface infrared spectroscopy. Surface Science Reports 8 211-357. 

The polymer concentration profile has been measured by small-angle neutron scattering from polymers adsorbed onto colloidal particles [70,71] or porous media [72] and from flat surfaces with neutron reflectivity [73] and optical reflectometry [74]. The fraction of segments bound to the solid surface is nicely revealed in NMR studies [75], infrared spectroscopy [76], and electron spin resonance [77]. An example of the concentration profile obtained by inverting neutron scattering measurements appears in Fig. XI-7, showing a typical surface volume fraction of 0.25 and layer thickness of 10-15 nm. The profile decays rapidly and monotonically but does not exhibit power-law scaling [70]. 

M. L. Hair, Infrared Spectroscopy in Surface Chemistry, Marcel Dekker, New York,... 

L. H. Little, Infrared Spectra of Adsorbed Molecules, Academic, New York, 1966. 68a. M. L. Hair, Infrared Spectroscopy in Surface Chemistry, Marcel Dekker, New... 

Still another type of adsorption system is that in which either a proton transfer occurs between the adsorbent site and the adsorbate or a Lewis acid-base type of reaction occurs. An important group of solids having acid sites is that of the various silica-aluminas, widely used as cracking catalysts. The sites center on surface aluminum ions but could be either proton donor (Brpnsted acid) or Lewis acid in type. The type of site can be distinguished by infrared spectroscopy, since an adsorbed base, such as ammonia or pyridine, should be either in the ammonium or pyridinium ion form or in coordinated form. The type of data obtainable is illustrated in Fig. XVIII-20, which shows a portion of the infrared spectrum of pyridine adsorbed on a Mo(IV)-Al203 catalyst. In the presence of some surface water both Lewis and Brpnsted types of adsorbed pyridine are seen, as marked in the figure. Thus the features at 1450 and 1620 cm are attributed to pyridine bound to Lewis acid sites, while those at 1540... 

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. 

Korzeniewski C 1997 Infrared spectroscopy in electrochemistry new methods and connections to UhV surface science Crit. Rev. Anai. Chem. 27 81... 

Surface species during the reaction were detected by Fourier transfonn infrared spectroscopy, using the Si-Cl... 

Leyden, D. E. Shreedhara Murthy, R. S. Surface-Selective Sampling Techniques in Pourier Transform Infrared Spectroscopy, Spectroscopy 1987, 2(2), 28-36. 

Whereas ATR spectroscopy is most commonly applied in obtaining infrared absorption spectra of opaque materials, reflection-absorption infrared spectroscopy (RAIRS) is usually used to obtain the absorption spectrum of a thin layer of material adsorbed on an opaque metal surface. An example would be carbon monoxide adsorbed on copper. The metal surface may be either in the form of a film or, of greaf imporfance in fhe sfudy of cafalysfs, one of fhe parficular crysfal faces of fhe mefal. 

Transmission Fourier Transform Infrared Spectroscopy. The most straightforward method for the acquisition of in spectra of surface layers is standard transmission spectroscopy (35,36). This approach can only be used for samples which are partially in transparent or which can be diluted with an in transparent medium such as KBr and pressed into a transmissive pellet. The extent to which the in spectral region (typically ca 600 4000 cm ) is available for study depends on the in absorption characteristics of the soHd support material. Transmission ftir spectroscopy is most often used to study surface species on metal oxides. These soHds leave reasonably large spectral windows within which the spectral behavior of the surface species can be viewed. 

Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy. Attenuated total redectance (atr) ftir spectroscopy is based on the principle of total internal redection (40). Methods based on internal redection in the uv and visible regions of the spectmm are also common in addition to those in the ir region. The implementation of internal redection in the ir region of the spectmm provides a means of obtaining ir spectra of surfaces or interfaces, thus providing moleculady-specific vibrational information. 

Several properties of the filler are important to the compounder (279). Properties that are frequentiy reported by fumed sihca manufacturers include the acidity of the filler, nitrogen adsorption, oil absorption, and particle size distribution (280,281). The adsorption techniques provide a measure of the surface area of the filler, whereas oil absorption is an indication of the stmcture of the filler (282). Measurement of the sdanol concentration is critical, and some techniques that are commonly used in the industry to estimate this parameter are the methyl red absorption and methanol wettabihty (273,274,277) tests. Other techniques include various spectroscopies, such as diffuse reflectance infrared spectroscopy (drift), inverse gas chromatography (igc), photoacoustic ir, nmr, Raman, and surface forces apparatus (277,283—290). 

High quahty SAMs of alkyltrichlorosilane derivatives are not simple to produce, mainly because of the need to carefully control the amount of water in solution (126,143,144). Whereas incomplete monolayers are formed in the absence of water (127,128), excess water results in facile polymerization in solution and polysiloxane deposition of the surface (133). Extraction of surface moisture, followed by OTS hydrolysis and subsequent surface adsorption, may be the mechanism of SAM formation (145). A moisture quantity of 0.15 mg/100 mL solvent has been suggested as the optimum condition for the formation of closely packed monolayers. X-ray photoelectron spectroscopy (xps) studies confirm the complete surface reaction of the —SiCl groups, upon the formation of a complete SAM (146). Infrared spectroscopy has been used to provide direct evidence for the hiU hydrolysis of methylchlorosilanes to methylsdanoles at the soHd/gas interface, by surface water on a hydrated siUca (147). 

Some of the techniques included apply more broadly than just to surfaces, interfaces, or thin films for example X-Ray Diffraction and Infrared Spectroscopy, which have been used for half a century in bulk solid and liquid analysis, respectively. They are included here because they have by now been developed to also apply to surfaces. A few techniques that are applied almost entirely to bulk materials (e.g.. Neutron Diffraction) are included because they give complementary information to other methods or because they are referred to significantly in the 10 materials volumes in the Series. Some techniques were left out because they were considered to be too restricted to specific applications or materials. 

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