Supported infrared spectroscopy

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. 

Italian investigators have recently shown by infrared spectroscopy that 3-hydroxy-5-phenylisoxazole exists as such and not in the isoxazolone form. This conclusion is supported by a spectroscopic investigation of the 4,5-dimethyl and other dialkyl analogs. ... 

There is supporting evidence in the literature for the validity of this method two cases in particular substantiate it. In one, tests were made on plastics heated in the pressure of air. Differential infrared spectroscopy was used to determine the chemical changes at three temperatures, in the functional groups of a TP acrylonitrile, and a variety of TS phenolic plastics. The technique uses a film of un-aged plastic in the reference beam and the aged sample in the sample beam. Thus, the difference between the reference and the aged sample is a measure of the chemical changes. 

Much earlier information on the structure of diazonium ions than that derived from X-ray analyses (but still useful today) was obtained by infrared spectroscopy. The pioneers in the application of this technique to diazonium and diazo compounds were Le Fevre and his school, who provided the first IR evidence for the triple bonds by identifying the characteristic stretching vibration band at 2260 cm-1 (Aroney et al., 1955 see also Whetsel et al., 1956). Its frequency lies between the Raman frequency of dinitrogen (2330 cm-1, Schrotter, 1970) and the stretching vibration frequency of the C = N group in benzonitrile (2255 cm-1, Aroney et al., 1955). In substituted benzenediazonium salts the frequency of the NN stretching vibration follows Hammett op relationships. Electron donor substituents reduce the frequency, whereas acceptor substituents increase it. The 4-dimethylamino group, for example, shifts it by 103 cm-1 to 2177 cm-1 (Nuttall et al., 1961). This result supports the hypothesis that... 

The identification of alkanesulfonates is possible by infrared spectroscopy. Computer-supported Fourier transform infrared spectroscopy (FT-IR) allows the... 

Transmission infrared spectroscopy is very popular for studying the adsorption of gases on supported catalysts and for studying the decomposition of infrared active catalyst precursors during catalyst preparation. Infrared spectroscopy is an in situ technique that is applicable in transmission or diffuse reflection mode on real catalysts. 

In order to investigate whether COj reacts in a concerted way with surface carbon or whether it dissociates first to CO and adsorbed oxygen and the adsorbed oxygen reacts, infrared spectroscopy, pulse reactor studies and XANES measuremerrts were used. The i.r. spectrum of a prereduced (Ihour at 675K in S /oHj/Nj) Pt/ZrOj catalyst in contact with CO2 at 775K is shown in Fig 6 The spectrum shows the presence of linearly bound CO on Pt at 2053 cm [15]. Additionally, bands of carbonate type species appeared in the region between 1375 and 1540 cm . Over pure supports (in the absence of Pt) the CO band was not seen, but peaks in the carbonate region were observed... 

For infrared spectroscopy, 20-50 mg of the cobalt-exchanged zeolite was pressed into a self-supporting wafer and placed into an infrared cell similar to that described by Joly et al. [21], Spectra were recorded on a Digilab FTS-50 Fourier-transform infrared spectrometer at a resolution of 4 cm-i. Typically, 64 or 256 scans were coadded to obtain a good signal-to-noise ratio. A reference spectrum of Co-ZSM-5 in He taken at the same temperature was subtracted from each spectrum. 

Figure 5.11 (Crisp Wilson, 1974b) shows the time-dependent variation of the concentration of soluble ions in setting and hardening cements. Note that the concentrations of aluminium, calcium and fluoride rise to maxima as they are released from the glass. After the maximum is reached the concentration of soluble ions decreases as they are precipitated. Note that this process is much more rapid for calcium than for aluminium and the sharp decline in soluble calcium corresponds to gelation. This indication is supported by information from infrared spectroscopy which showed that gelation (initial set) was caused by the precipitation of calcium polyacrylate. This finding was later confirmed by Nicholson et al. (1988b) who, using Fourier transform infrared spectroscopy (FTIR), found that calcium polyacrylate could be detected in the cement paste within one minute of mixing the cement. There was no evidence for the formation of any aluminium polyacrylate within nine minutes and substantial amounts are not formed for about one hour (Crisp et al, 1974).

The strength of the Bronsted (BAS) and Lewis (LAS) acid sites of the pure and synthesized materials was measured by Fourier transformed infrared spectroscopy (ATI Mattson FTIR) by using pyridine as a probe molecule. Spectral bands at 1545 cm 1 and 1450 cm 1 were used to indentify BAS and LAS, respectively. Quantitative determination of BAS and LAS was calculated with the coefficients reported by Emeis [5], The measurements were performed by pressing the catalyst into self supported wafers. Thereafter, the cell with the catalyst wafer was outgassed and heated to 450°C for lh. Background spectra were recorded at 100°C. Pyridine was then adsorbed onto the catalyst for 30 min followed by desorption at 250, 350 and 450°C. Spectra were recorded at 100°C in between every temperature ramp. 

Rasmussen [82] describes a gas chromatographic analysis and a method for data interpretation that he has successfully used to identify crude oil and bunker fuel spills. Samples were analysed using a Dexsil-300 support coated open tube (SCOT) column and a flame ionisation detector. The high-resolution chromatogram was mathematically treated to give GC patterns that were a characteristic of the oil and were relatively unaffected by moderate weathering. He compiled the GC patterns of 20 crude oils. Rasmussen [82] uses metal and sulfur determinations and infrared spectroscopy to complement the capillary gas chromatographic technique. 

Several forms of infrared spectroscopy are in use, as illustrated in Fig. 8.4. The most common form of the technique is transmission infrared spectroscopy. In this case the sample consists typically of 10-100 mg of catalyst, pressed into a self-supporting disk of approximately 1 cm2 and a few tenths of a millimeter in thickness. Transmission IR can be applied if the bulk of the catalyst absorbs weakly. This is usually the... 

Carbon monoxide on metals forms the best-studied adsorption system in vibrational spectroscopy. The strong dipole associated with the C-O bond makes this molecule a particularly easy one to study. Moreover, the C-0 stretch frequency is very informative about the direct environment of the molecule. The metal-carbon bond, however, falling at frequencies between 300 and 500 cm1, is more difficult to measure with infrared spectroscopy. First, its detection requires special optical parts made of Csl, but even with suitable equipment the peak may be invisible because of absorption by the catalyst support. In reflection experiments on single crystal surfaces the metal-carbon peak is difficult to obtain because of the low sensitivity of RAIRS at low frequencies [12,13], EELS, on the other hand, has no difficulty in detecting the metal-carbon bond, as we shall see later on. 

Note that in all the examples discussed so far, infrared spectroscopy gives its information on the catalyst in an indirect way, via hydroxyl groups on the support, or via the adsorption of probe molecules such as CO and NO. The reason why it is often difficult to measure the metal-oxide or metal-sulfide vibrations of the catalytically active phase in transmission infrared spectroscopy is that the frequencies are well below 1000 cm-1, where measurements are difficult because of absorption by the support. Infrared emission and Raman spectroscopy, discussed later on in this chapter, offer better opportunities in this respect. 

The structure of supported rhodium catalysts has been the subject of intensive research during the last decade. Rhodium is the component of the automotive exhaust catalyst (the three-way catalyst) responsible for the reduction of NO by CO [1], In addition, it exhibits a number of fundamentally interesting phenomena, such as strong metal-support interaction after high temperature treatment in hydrogen [21, and particle disintegration under carbon monoxide [3]. In this section we illustrate how techniques such as XPS, STMS, EXAFS, TEM and infrared spectroscopy have led to a fairly detailed understanding of supported rhodium catalysts. 

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... 

Bazin et al.447 applying infrared spectroscopy and CO adsorption to a Pt/ceria catalyst, assigned a band at 1937 cnC1 on the reduced catalyst to a bridging CO species bound between both the support and Pt particle. 

The present procedure2 describes the conversion of resin-bound, primary aliphatic amines into isothiocyanates and the conversion of the latter into 3-aminothiophenes. The generation of isothiocyanates is related to known procedures,3 in which amines are first treated with carbon disulfide and the resulting dithiocarba-mates are desulfurized by treatment with a condensing agent (alkyl chloroformates, carbodiimides, lead or mercury salts, etc.). The presence of resin-bound isothiocyanates on the polystyrene support could be qualitatively ascertained by infrared spectroscopy (KBr-pellet strong absorption at 2091 cm-1). 

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