Mixed oxide catalyst supports

Strength (FLS) empirical approach are discussed in Section 3 as methods for determining the molecular structures of metal-oxide species from their Raman spectra. The state-of-the-art in Raman instrumentation as well as new instrumental developments are discussed in Section 4. Sampling techniques typically employed in Raman spectroscopy experiments, ambient as well as in situ, are reviewed in Section S. The application of Raman spectroscopy to problems in heterogeneous catalysis (bulk mixed-oxide catalysts, supported metal-oxide catalysts, zeolites, and chemisorption studies) is discussed in depth in Section 6 by selecting a few recent examples from the literature. The future potential of Raman spectroscopy in heterogeneous catalysis is discussed in the fmal section. 

Fig. 1. Examples of the kinetic curves during ethylene polymerization by chromium oxide catalysts. Support—SiOs temperature—80°C polymerization at constant ethylene pressure in perfect mixing reactor. Curve 1—catalyst reduced by CO at 300°C. Curve 2— catalyst activated in vacuum (400°C) polymerization in the case of (1) and (2) in solvent (heptane) ethylene pressure 10 kg/cm2 02 content in ethylene 1 ppm, HsO 3 ppm. Curves 3, 4, 5, 6—catalyst activated in vacuum (400°C) polymerization without solvent ethylene pressure 19 (curve 3), 13 (curve 4), 4 (curve 5), and 2 (curve 6) kg/cm2 02 content in ethylene 1 ppm, HsO = 12 ppm.

An iron phosphate catalyst with a P/Fe atomic ratio of 1.2 used in this study was prepared according to the procedures described in the previous studies [6-8]. On the other hand, a V-P oxide catalyst with a P/V atomic ratio of 1.06 and pumice supported 12-molybdophosphoric acid (H3PM012O40) and its cesium salt (CS2HPM012O40) catalysts were the same as used in a previous study [9]. Pumice supported W03-based mixed oxide catalysts were the same as used in a previous study [10]. 

The samples prepared have a good surface area after calcination at 500°C, as can be seen in table 1. Alumina-titania mixed oxide supported samples have surface areas larger than those of the alumina and titania single oxides. As expected x-ray diffraction results show that the mixed oxide catalysts are amorphous, but alumina shows a y phase structure, and Ti02 is a well crystallized anatase phase. No nickel metal or nickel oxide was detected in any of the samples, including Ti02 sample, suggesting the metal was well dispersed, and present as small crystallites (< 50A). 

Another important consideration in preparing mixed-oxide catalysts is the spontaneous monolayer dispersion of oxides and salts onto surfaces of support substrates on calcination. Both temperature and duration of calcination are important here, as discussed in the reviews by Xie and Tang [63] and by Knozinger and Taglauer [64]. If this dispersion step is inadequate or incomplete, the resulting oxide layer, and any reduced metal surface from it, will not be reproducible from the same catalyst system therefore, one can then have different catalysts prepared at different times and, of course, from one laboratory to another. Spreading and wetting phenomena in preparation of supported catalysts is discussed in Section A.2.2.1.3. 

A recent in situ Mossbauer study (124) of a mixed tin-platinum oxide catalyst supported on zinc aluminate at 500°-600°C indicated the presence of tin(IV), tin(II), and an alloy of tin and platinum in the active catalyst. Changes in the nature of the tin species with time and temperature were correlated with the catalytic activity of the material. 

Furan has also been labeled with heavy water on supported catalysts (chromium, zinc, and manganese oxides promoted with K2C03) at a temperature of 350°.117 Deuterated furan has also been obtained from the vapor phase decarbonylation of furfural over mixed oxide catalysts in the presence of heavy water. Both of these systems utilize extreme experimental conditions and the methods outlined in Table XII are to be preferred for preparative labeling. 

Beckler, R. K. and M. G. White, Polynuclear Metal Complexes as Model Mixed Oxide Catalysts Selective Chemisorption of NH3 and NO , J. Catal, 109, pp. 25-36 (1988) Beckler, R. K. and M. G. White, Polynuclear Metal Complexes as Model Mixed Oxide Catalysts Isomerization Activity , J. Catal, 110, pp. 364-374 (1988). Coulier, L., V. G. Kishan, J. A. R. van Veen, and J W. Niemantsverdriet, Surface science models for CoMo Hydrodesulfurization Catalysts the Influence of the support on hydrodesulfurization acidity , J. Vac Scl Technol A. 19, Issue 4, 1 July/August 2001, pp 1510-5. 

Among the families of solid bases, we have particularly studied three of them. The first two ones (MgLa mixed oxides and supported alkali fluorides) were applied to fine chemistry while in the third case (CuO), the role of the basic strength of this oxidant on the selective adsorption of NO in the NOx trap technology has been studied. In each case, a fundamental effeet of the active species dispersion on the catalyst basic strength and reactivity has been found. 

In a series of papers published by Swedish and Japanese researchers, they used supported and massive perovskites of the general formula Lai xSrxM 2l Cul,Rul,03 (M = A1, Mn, Fe or Co) as catalysts for the reduction of NO with CO. Skoglundh et al. (1994) prepared nine alumina washcoated mixed oxide catalysts containing La, Sr, Cu and Ru. The solids obtained were thoroughly characterized using several techniques. They were tested in two different reactant streams (i) N0/C0/C3H6/02/N2 (feed stream A) and (ii) NO/CO/N2 (feed stream B). 

An unexpected result was the progressive apparent dechlorination of SiOTiCla. We have verified that this phenomenon was not related to the presence or absence of TiCU either physically adsorbed or in the gas phase. We could also observe the growth of the same IR bands between 1000 and 600 cm using a self-supporting disc. Therefore, the dechlorination of TiCU on silica and the eventual incorporation of Ti as a random mixed metal surface oxide is probably entropy driven. Although the initial chemisorption follows reaction (3) and (4), further dechlorination probably results in the formation of SiCl surface species. The vibrations of this near 7(X) cm would be impossible to detect with a thin film given the low extinction coefficient [15], and in any case, they would be masked by the much stronger SiOTi vibrations. Finally, the results have implications for mixed oxide catalysts which are prepared by chemical vapor deposition. Structural models which are based on the notion that only reactions like those depicted in schemes (3) and (4) occur are probably not valid. 

These reactions may occur simultaneously or not, depending on the thermodynamic conditions and especially on the catalyst. In the methanation Ni, catalysts are used, while in Fischer-Tropsch reactions, Fe or Co catalysts are employed. In the reactions for methanol synthesis, mixed oxide catalysts of CuO/ZnO are used, and for the shift reaction, Ni supported catalyst. 

In Fig. 7.6, the EPR spectra of the Ti02—supported monometallic and mixed oxide catalysts are compared [52]. Surprisingly, the introduction of tungsten strongly suppressed the isotropic signal from the surface V oxide islands. The effect is drastic, because the coverages in the mixed systems are very high due to... 

Co-based catalysts, such as CoOjc-Ce02 mixed oxides, CoO supported over alumina, and CoMgAl and CoNiAl hydrotalcites are also active in the reaction. Between these, the CoNiAl material shows the highest activity for the conversion... 

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