Infrared spectroscopy active site

Owing largely to research over the last twenty years, the sulfided C0-M0/AI2O3 system is one of the best-characterized industrial catalysts [H. Topsoe, B.S. Clausen and F.E. Massoth, Hydrotreating Catalysis (1996), Springer-Verlag, Berlin]. A combination of methods, such as Mbssbauer spectroscopy, EXAFS, XPS, and infrared spectroscopy, has led to a picture in which the active site of such a catalyst is known in almost atomic detail. 

Active centers, nature of, 10 96 Active site, 27 210-221 in catalysts, 17 103-104, 34 1 for olefin chemisorption, 17 108-113 dual-site concept, 27 210 electrical conductivity, 27 216, 217 ESCA, 27 218, 219 ESR, 27 214-216 infrared spectroscopy, 27 213, 214 model, 27 219-221 molybdena catalyst, 27 304-306 Mdssbauer spectroscopy, 27 217, 218 nonuniform distribution, transport-limited pellets, 39 288-291... 

The admixture of lead to platinum has a similar effect (Fig. 5). At the same time, the aromatizing activity increases up to about 1 1 Pt Pt atomic ratio 24). With even more lead it scatters aroimd somewhat lower values 66). Electron donation from lead to platinum has been proved by infrared spectroscopy, so one may wonder whether lead is present as metal in the catalyst (75). The additive effect can also be interpreted by its creating hydrogen-deficient surface sites favorable for aromatization. When more lead is present than platinum (i.e., where no more continuous platinum surface is probable), the inverse correlation between hydrogen adsorptivity and activity ceases to exist. 

Adsorption of NH3 on hematite followed a Langmuir isotherm and had a heat of adsorption of 48.3 kj mol (Blyholder and Richardson, 1962). Infrared spectroscopy indicated that coordination involved the Lewis acid sites on (activated) hematite (Rochester and Topham, 1979 b). 

The catalytically active sites of isomorphous substituted MFI structures (Al-Sil and In-Sil) have been characterized by infrared spectroscopy and microcalorimetric measurements using ammonia and acetonitrile as probes [261]. The hrst derivative of the heat of adsorption curves, dg/dfl, as function of the loading, a, gave maxima at about 140 and 100 kJ/mol for Al-Sil and In-Sil, respectively. Janchen and colleagues... 

The nature of the titanium-containing active site has been investigated with different techniques, including theoretical calculations. The formation of a hydroperoxidic species or of a bidentate side-on titanium peroxo structure was suggested by many authors . Alternatively, some DFT calculations indicated an undissociated molecule of H2O2 weakly interacting with Ti centers or an active Ti-O-O-Si peroxo moiety as a reactive site . Recently, Lin and Frei reported the first direct detection, obtained using in situ FT-infrared spectroscopy, of a Ti-OOH moiety as active species in the oxidation of small olefins like ethylene or propylene . 

There is considerable evidence that surface acidity influences the catalytic activity of iron molybdate [254]. It was found by studying the adsorption of ammonia using infrared spectroscopy that, under reaction conditions, the acidity is due to Lewis sites. The conclusion is that surface acidity is a necessary, but not a sufficient, property. 

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