Infrared spectroscopy of surface

Dannenberg, H., et al., Infrared Spectroscopy of Surface Coatings in Reflected Light, Analytical Chemistry, March 1960. 

Inelastic effects are exploited in the rapidly developing technique of high resolution electron energy loss spectroscopy (ELS or EELS) which permits identification of adsorbed molecules or molecular fragments by their vibrational spectra. Thus the method has much in common with the infrared spectroscopy of surfaces and, not surprisingly, the classic case of CO adsorption has received attention on Ni(lOO) and on stepped Ni and Pt surfaces. Other recent investigations of interest include H2 on organic species on Ni and Pt, and the observation of... 

Kiselev, A. V. Lygin, V. I. Infrared Spectroscopy of Surface Compounds Wiley Interscience New York, 1975. 

N.K. Roberts. Fourier Transform Infrared Spectroscopy of Surfaces. In D.J. O Conner, B.A. Sexton, and R. St. C. Smart, editors. Surface Analysis Methods in Materials Science. Springer Series in Surface Sciences, Volume 23. Springer-Verlag, Berlin, 1992. 

I. N. PlaksinandV. I. So t ys ikm, Infrared Spectroscopy of Surface Layers on Minerals, Nauka, Moscow, 1966. 

Diffuse reflectance infrared spectroscopy of surface complexes. 

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

A. A. Davydov, Infrared spectroscopy of adsorbed species on the surfaces of transition metal oxides, Wiley, Chichester, 1990. 

Beden B, Juanto S, Leger JM, Lamy C. 1987. Infrared spectroscopy of the methanol adsorbates at a platinum electrode Part III. Structural effects and behaviour of the polycrystalline surface. J Electroanal Chem 238 323-331. 

M. Claybourn, Infrared Spectroscopy of Polymers Analysis of Films, Surfaces and Interfaces, Global Press, Chicago, 1998. 

As already indicated above, what one may consider a surface depends on the property under consideration. Adhesion is very much an outer atomic layer issue, unless one is dealing with materials like fibreboard in which the polymer resin may also be involved in mechanical anchoring onto the wood particles. Gloss and other optical properties are related to the penetration depth of optical radiation. The latter depends on the optical properties of the material, but in general involves more than a few micrometer thickness and therewith much more than the outer atomic layers only. It is thus the penetration depth of the probing technique that needs to be suitably selected with respect to the surface problem under investigation. Examples selected for various depths (< 10 nm, 10 s of nm, 100 nm, micrometer scale) have been presented in Chapter 10 of the book by Garton on Infrared Spectroscopy of Polymer Blends, Composites and Surfaces... 

The use of infrared spectroscopy of adsorbed molecules to probe oxide surfaces has been reviewed by Davydov and Rochester [23], This approach works on sulfide catalysts as well. The infrared signal of NO has been successfully used to identify sites on the surface of a hydrodesulfurization catalyst, as the following example shows [24]. 

A.A. Davydov and C.H. Rochester, Infrared Spectroscopy of Adsorbed Species on the Surface of Transition Metal Oxides, Wiley, New York, 1990. 

Edwards and Schrader—IR investigations support common formate intermediate in water-gas shift and methanol synthesis over Cu/ZnO. Edwards and Schrader,234 using careful reduction procedures (95%N2/5%H2), were able to obtain direct evidence by infrared spectroscopy of the formation of active OH groups on Cu/ZnO, that formed surface formates on the surface of the zinc phase (1576, 1381, 1366, 2970, and 2878 cm-1, respectively for OCO asymmetric, OCO symmetric, and C-H stretching bands) upon exposure to CO. In the presence of CO and H20, the formate intensity initially increased, followed by the production of C02, indicative of water-gas shift. A carbonyl band was also observed at 2093 cm-1. The authors... 

Obviously, there is still much interesting work to be done on infrared spectroscopy of molecules adsorbed on metal surfaces in the future, both for those interested in instrumental development as well as those who will use the technique as one of many surface science tools. 

Infrared Spectroscopy of Molecules Adsorbed on Metal Surfaces 1... 

Ballinger, T.H., Wong, J.C.S., and Yates, J.T., Jr. (1992) Transmission infrared spectroscopy of high area solid surfaces. A usefid method for sample preparation. Langmuir, 8, 1575-1578. 

Lamberti, C., Groppo, G., Spoto, S., Bordiga, S., and Zecchina, A. (2007) Infrared spectroscopy of transient surface species. Adv. Catal, 51,1-74. 

Isupova, LA Budneva, AA Paukshtis, EA Sadykov, VA. Nature of the perovskites surface centers as studied by the Infrared spectroscopy of adsorbed NO test molecule. J. Mol. Catal, A Chem., 2000, Volume 158, Issue 1, 275-280. 

A. Garton, Infrared Spectroscopy of Polymer Blends, Composites and Surfaces, Hanser, Munich (1992)... 

Chabal, Y. J. High-resolution infrared spectroscopy of adsorbates on semiconductor surfaces hydrogen on Si(100) and Ge(100). Surface Science 168, 594—608 (1986). 

The most powerful tool for the characterization of acidic groups in solid surfaces is infrared spectroscopy. Since this method enables the measurement of the extent of protonation of a chemisorbed base, the chief handicap of the previously described methods has been overcome the amount of basic reagent required to neutralize Br0nsted acids can be distinguished from that attached to a catalyst surface by other types of chemical bonds. Several general reviews are already available that deal with the infrared spectroscopy of solid surfaces (37-39). Our discussions of this tool will therefore be limited to some of the highlights in the application of infrared spectroscopy for the determination of surface acidity. 

Interest in the vibrational spectra of adsorbed molecules is at least 40 years old. The past ten years have seen the development of many novel techniques for determining the vibrational spectra of adsorbed species and this symposium brings together a state-of-the-art survey of these techniques. In one s ethusiasm for the recent advances made in any subject there is a tendency to forget the parent technique and its steady contribution to our knowledge. In this case, the parent is simple transmission infrared spectroscopy. This paper, therefore, is an attempt to briefly present an overview of some of the developments which have occurred in the application of transmission infrared spectroscopy to surface studies with emphasis upon results generated in the past 10 years. For more detailed information on work published prior to 1967 the reader is referred to three texts which have appeared on this subject (1-3). 

Bailey, R. B. and Richards, P. L., "Infrared Absorption Spectroscopy of Surfaces A Low Temperature Detection Scheme" Lawrence Berkeley Laboratory Report LBL-7639 Berkeley, CA, 1979. 

The identification of species adsorbed on surfaces has preoccupied chemists and physicists for many years. Of all the techniques used to determine the structure of molecules, interpretation of the vibrational spectrum probably occupies first place. This is also true for adsorbed molecules, and identification of the vibrational modes of chemisorbed and physisorbed species has contributed greatly to our understanding of both the underlying surface and the adsorbed molecules. The most common method for determining the vibrational modes of a molecule is by direct observation of adsorptions in the infrared region of the spectrum. Surface spectroscopy is no exception and by far the largest number of publications in the literature refer to the infrared spectroscopy of adsorbed molecules. Up to this time, the main approach has been the use of conventional transmission IR and work in this area up to 1967 has been summarized in three books. The first chapter in this volume, by Hair, presents a necessarily brief overview of this work with emphasis upon some of the developments that have occurred since 1967. 

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