Infrared spectroscopy molecular adsorption

Infrared Spectroscopy. The infrared spectroscopy of adsorbates has been studied for many years, especially for chemisorbed species (see Section XVIII-2C). In the case of physisorption, where the molecule remains intact, one is interested in how the molecular symmetry is altered on adsorption. Perhaps the conceptually simplest case is that of H2 on NaCl(lOO). Being homo-polar, Ha by itself has no allowed vibrational absorption (except for some weak collision-induced transitions) but when adsorbed, the reduced symmetry allows a vibrational spectrum to be observed. Fig. XVII-16 shows the infrared spectrum at 30 K for various degrees of monolayer coverage [96] (the adsorption is Langmuirian with half-coverage at about 10 atm). The bands labeled sf are for transitions of H2 on a smooth face and are from the 7 = 0 and J = 1 rotational states Q /fR) is assigned as a combination band. The bands labeled... 

Adsorption phenomena from solutions onto sohd surfaces have been one of the important subjects in colloid and surface chemistry. Sophisticated application of adsorption has been demonstrated recently in the formation of self-assembhng monolayers and multilayers on various substrates [4,7], However, only a limited number of researchers have been devoted to the study of adsorption in binary hquid systems. The adsorption isotherm and colloidal stabihty measmement have been the main tools for these studies. The molecular level of characterization is needed to elucidate the phenomenon. We have employed the combination of smface forces measmement and Fomier transform infrared spectroscopy in attenuated total reflection (FTIR-ATR) to study the preferential (selective) adsorption of alcohol (methanol, ethanol, and propanol) onto glass surfaces from their binary mixtures with cyclohexane. Om studies have demonstrated the cluster formation of alcohol adsorbed on the surfaces and the long-range attraction associated with such adsorption. We may call these clusters macroclusters, because the thickness of the adsorbed alcohol layer is about 15 mn, which is quite large compared to the size of the alcohol. The following describes the results for the ethanol-cycohexane mixtures [10],... 

Much of the pioneering work which led to the discovery of efficient catalysts for modern Industrial catalytic processes was performed at a time when advanced analytical Instrumentation was not available. Insights Into catalytic phenomena were achieved through gas adsorption, molecular reaction probes, and macroscopic kinetic measurements. Although Sabatier postulated the existence of unstable reaction Intermediates at the turn of this century. It was not until the 1950 s that such species were actually observed on solid surfaces by Elschens and co-workers (2.) using Infrared spectroscopy. Today, scientists have the luxury of using a multitude of sophisticated surface analytical techniques to study catalytic phenomena on a molecular level. Nevertheless, kinetic measurements using chemically specific probe molecules are still the... 

In situ infrared spectroscopy allows one to obtain stracture-specific information at the electrode-solution interface. It is particularly useful in the study of electrocat-alytic reactions, molecular adsorption, and the adsorption of ions at metal surfaces. 

At present, most workers hold a more realistic view of the promises and difficulties of work in electrocatalysis. Starting in the 1980s, new lines of research into the state of catalyst surfaces and into the adsorption of reactants and foreign species on these surfaces have been developed. Techniques have been developed that can be used for studies at the atomic and molecular level. These techniques include the tunneling microscope, versions of Fourier transform infrared spectroscopy and of photoelectron spectroscopy, differential electrochemical mass spectroscopy, and others. The broad application of these techniques has considerably improved our understanding of the mechanism of catalytic effects in electrochemical reactions. 

Vibrational spectroscopy provides the most definitive means of identifying the surface species arising from molecular adsorption and the species generated by surface reaction, and the two techniques that are routinely used for vibrational studies of molecules on surfaces are Infrared (IR) Spectroscopy and Electron Energy Loss Spectroscopy (HREELS) (q.v.). 

Spectroscopic techniques may provide the least ambiguous methods for verification of actual sorption mechanisms. Zeltner et al. (Chapter 8) have applied FTIR (Fourier Transform Infrared) spectroscopy and microcalorimetric titrations in a study of the adsorption of salicylic acid by goethite these techniques provide new information on the structure of organic acid complexes formed at the goethite-water interface. Ambe et al. (Chapter 19) present the results of an emission Mossbauer spectroscopic study of sorbed Co(II) and Sb(V). Although Mossbauer spectroscopy can only be used for a few chemical elements, the technique provides detailed information about the molecular bonding of sorbed species and may be used to differentiate between adsorption and surface precipitation. 

Applying in situ infrared spectroscopy and STM, Cai et al. [253] have studied adsorption of pyridine on Au(lll) electrodes from aqueous NaCl04 solutions. It has been found that pyridine molecule is flatly adsorbed on the surface at negative potentials. Its molecular plane rises up as the applied potential and surface concentration increase. Moreover, orientation of pyridine molecule changed with the applied STM potential. Ikezawa et al. [243] have used in situ FTIR spectroscopy to investigate adsorption of pyridine on Au(lll), Au(lOO),... 

Fourier-transformed infrared spectroscopy (FT1R), either in the transmission mode(70), the grazing incidence reflection (GI) mode(7,5) or the attenuated total reflection (ATR) mode(7,2), has been the most widely used experimental tool for the characterization and structure determination of SA monolayers. GI-IR is especially useful in determining the molecular orientation in the film structures because it senses only the vibrational component perpendicular to the substrate surface(7,5). Polarized ATR-IR can also be used to study molecular orientation(7,77). McKeigue and Gula-ri(72) have used ATR-IR to quantitatively study the adsorption of the surfactant Aerosol-OT. 

Thus, adsorption of NH3 on alumina resembles that of water in many respects. Both molecules are adsorbed molecularly at low temperatures but are chemisorbed dissociatively at higher temperatures. Ammonia is held strongly on A1203 surfaces and cannot be removed completely even on desorption at 500°C. Various species occur simultaneously, their relative importance being determined by the OH content of the surface. Furthermore, displacement adsorptions may take place. Thus, NH2" ions readily replaced chloride ions on surfaces of chlo-rided aluminas (166). One has, therefore, to conclude that ammonia retention on aluminas cannot be an acceptable measure of surface acidity and can hardly be related to catalytic activity. Ammonia adsorption on aluminas as studied by infrared spectroscopy, perhaps combined with TPD experiments (173), gives ample information on surface properties but ammonia cannot be used as a specific poison on alumina. 

Differences in adsorption behavior on air-dried and flamed silica are attributed to differences in the rate at which water within the silica can diffuse to the surface—the rate being much less for the flamed surfaces. Therefore, any adsorbed molceular water that is removed from the air-dried surfaces as a result of polymer formation (Postulate 4) will be quickly replaced by molecular water held in the silica immediately below die surface. On the other hand, for flamed silica the rate of replacement is believed to be much slower. In general the presence of molecular water in glass and in fused silica surfaces is well established (6) and preliminary studies using infrared spectroscopy confirm its presence in the silica plates used here. Flaming would remove a large portion of this interior water from the first one or two microns below the surface. 

Carbondioxide adsorption is another example of molecular adsorption which has been studied quite extensively in the past. While for some time is was generally accepted that CO2 forms carbonates with chromia surfaces very readily upon exposure, it was recently observed that carboxylate species may be formed. TDS spectra indicate [111, 112] that there are more weakly and less weakly bound CO2 species on the surfaces. We have studied the nature of those species by various techniques including infrared spectroscopy. Fig. 23 shows several sets of IR spectra. The pair of sharp bands around 2300 cm can easily be assigned to the more weakly bound CO2 with only slightly distorted structure... 

Up to now, infrared spectroscopy has been used mainly to determine the types of hydroxyl groups and the acidity of zeolites (39). The frequencies of the vertical and horizontal vibrations (with respect to the cavity wall) of H2O molecules adsorbed in zeolite A were determined by measurements in the far infrared ( 220 and —75 cm" ) (37). These values are in agreement with a simple theoretical model. A number of ultraviolet and ESR studies are reviewed (33). The difference has been established between the specific molecular interaction of aromatic molecules on zeolites cationized with alkali cations and the more complex interactions involving charge transfer in CaX and deca-tionized X and Y zeolites. These more complex interactions with CaX zeolites containing protonized vacancies and with decationized zeolites are similar. These phenomena are related to the interactions of molecules with acidic centers in zeolites which are stronger, as compared with the molecular adsorption. 

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... 

A study of methanol adsorption on platinum under UHV conditions or at a gas/solid interface is also of interest. Not many papers dealing with methanol adsorption in a UHV chamber [135,136] are available. The adsorption takes place without a reaction on Pt( 111) at lo w temperatures (100 K), and based on thermal desorption experiments it was concluded that a monolayer of methanol adsorbate desorbs at 180 K. The heat of adsorption of molecular methanol was estimated to be 46 kJ mol-1 on unreconstructed Pt(l 11) [137]. Infrared spectroscopy has been applied for the study of methanol adsorption on Pt(l 11) [138], and it was shown that a 0.36 monolayer of methanol corresponds to the saturation of the desorption peak found at 180 K. The methanol multilayer coverages were also found, but had different infrared frequencies that were associated with the methyl and C-0 stretching modes (Scheme 11.1). 

Synthesis of mesoporous molecular sieves MCM-41 and MCM-48 was carried out under microwave and hydrothermal conditions. Molecular sieves prepared were characterized using X-ray powder diffraction, scanning electron microscopy, nitrogen adsorption isotherms and infrared spectroscopy to evaluate the properties of these materials. It was observed that mesoporous molecular sieves synthesized under microwave conditions exhibit higher activity in oxidation of adamantanone by hydrogen peroxide to the respective lactone (Baeyer-Villiger oxidation). 

Infrared spectroscopy using the adsorption of infrared radiation by the molecular bonds to identify the bond types which can absorb energy by vibrating and rotating. In FT-IR the need for a mechanical slit is eliminated by frequency modulating one beam and using interferometry to choose the infrared band. 

Infrared spectroscopy has continued to support the study of adsorption and reactivity at well-defined electrode surfaces. Single crystals are employed to probe active site models for catalytic reactions and as templates for the deposition and growth of other phases. Infrared spectroscopy has played an important role in enabling in-situ detection and molecular-level characterization of species present at these surfaces. The sections below highlight some recent areas of apphcation. 

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