Supported metal oxide

Oxide-supported metals constitute one of the most important classes of heterogeneous catalysts, and for this reason they have been investigated by many techniques adsorption isotherms, IR of chemisorbed molecules, electron microscopy, EXAFS, etc. Flowever, the fact that they have been studied by so many methods proves that no one technique is totally satisfactory. 

The decarbonylation of oxide-supported metal carbonyls yields gaseous products including not just CO, but also CO2, H2, and hydrocarbons [20]. The chemistry evidently involves the support surface and breaking of C - O bonds and has been thought to possibly leave C on the clusters [21]. The chemistry has been compared with that occurring in Fischer-Tropsch catalysis on metal surfaces [20] support hydroxyl groups are probably involved in the chemistry. 

NMR spectroscopy has been used to detect hydrides on various oxide-supported metals in the presence of H2 and on La203-supported Ir4, in the absence of H2 [37]. The kinetics of chemisorption of H2 supports the inference of hydride formation by dissociative adsorption of H2 [38]. 

Nanoparticle Geometry at Oxide-supported Metal Catalysts... 

Figure 2.10 Trajectory of an STM tip above an oxide-supported metal particle.

Zheng, N.F. and Stucky, G.D. (2006) Ageneral synthetic strategy for oxide-supported metal nanoparticle catalysts. Journal of the American Chemical Society, 128 (44), 14278-14280. 

The lack of calorimetric data is particularly evident in the case of the adsorption of gases on oxides or on oxide-supported metals, i.e., on solids similar to most industrial catalysts. Moreover, adsorption calorimeters are generally used at temperatures that are much lower than those usually found in industry, and it would be difficult indeed to adapt most usual adsorption calorimeters for the measurement of heats of adsorption of gases on industrial catalysts at elevated temperatures. The present success of gas chromatographic techniques for determining heats of reversible adsorption may be explained by the gap between the possibilities of the usual adsorption calorimeters and the requirements of industrial catalysis research. 

It is true, however, that many catalytic reactions cannot be studied conveniently, under given conditions, with usual adsorption calorimeters of the isoperibol type, either because the catalyst is a poor heat-conducting material or because the reaction rate is too low. The use of heat-flow calorimeters, as has been shown in the previous sections of this article, does not present such limitations, and for this reason, these calorimeters are particularly suitable not only for the study of adsorption processes but also for more complete investigations of reaction mechanisms at the surface of oxides or oxide-supported metals. The aim of this section is therefore to present a comprehensive picture of the possibilities and limitations of heat-flow calorimetry in heterogeneous catalysis. The use of Calvet microcalorimeters in the study of a particular system (the oxidation of carbon monoxide at the surface of divided nickel oxides) has moreover been reviewed in a recent article of this series (19). 

D.C. Meier, X. Lai, and D.W. Goodman, Surface chemistry of model oxide-supported metal catalysts An overview of gold on Titania, in Surface Chemistry and Catalysis, eds. A.F. Carley et al. Kluwer, New York, 2002, pp. 147-189. 

O2 adsorption, 28 38 surface modility, 28 34 surface structure, 28 30, 31 oxidation of CO on, 28 65 oxide-supported metal catalysts, 41 10, 11 -phosphine catalysts achiral, 25 83-85 recovery, 32 354-356, 367-369 selectivity, 30 348 platinum, 30 355 -silica catalysts... 

Oxide-Supported Metal Thin-Film Catalysts The How and Why... 

Oxide-supported metals play an important role in a wide variety of industrial chemical processes such as the catalytic treatment of automotive exhaust. The ability to exercise greater control over the interactions of molecules on metal surfaces will create new possibilities for pollution control and the provision of novel power sources. Furthermore, a deeper understanding of molecule surface interactions will present numerous opportunities for the design of nanocatalysts. 

OXIDE-SUPPORTED METAL THIN-FILM CATALYSTS... 

Recent Advances on NO Reduction Related to Mixed Oxides, Supported Metals and Ion-Exchange Mesoporous... 

The presence of oxygen enhances the catalyst stability. Breen et al. [187] investigated SRE over a range of oxide-supported metal catalysts. They concluded that the support plays an important role in the reaction. In fact, they observed that alumina-supported catalysts are very active at low temperatures for dehydration of ethanol to ethylene, which at higher temperatures (550 °C) is converted into H2, CO and CO2 as major products and CH4 as a minor product. The activities of the metal decrease in the order of Rh > Pd > Ni PS Pt. Ceria/zirconia-supported catalysts are more active and exhibit 100% conversion of ethanol at high space velocity and high temperature (650 °C). 

The literature of the vibrational spectra of adsorbed alkynes (acetylene and alkyl-substituted acetylenes) is very much in favor of single-crystal studies, with fewer reported investigations of adsorption on oxide-supported metal catalysts. Fewer studies still have been made of the particulate metals under the more advantageous experimental conditions for spectral interpretation, namely, at low temperatures and on alumina as the support. (The latter has a wide transmittance range down to ca. 1100 cm-1.) A similar number of different single-crystal metal surfaces have been studied for ethyne as for ethene adsorption. We shall review in more detail the low-temperature work which usually leads to HCCH nondissociatively adsorbed surface structures. Only salient features will be discussed for higher temperature ethyne adsorption that often leads to dissociative chemisorption. Many of the latter species are those already identified in Part I from the decomposition of adsorbed ethene. 

In a few cases, adsorption on particulate nickel has been studied other than in the form of the conventional oxide-supported metal catalysts. Nash and De Sieno (73) exploded nickel wires in a rare-gas atmosphere to give Ni particles of ca. 20-nm diameter. Results were reported (but not illustrated) characterizing adsorption of ethyne they are similar to those found by Eischens and Pliskin. 

Surprisingly, the literature seems to record only a single infrared study of propyne adsorption on a metal oxide-supported metal, Pt/Si02, where the silica support was in the form of porous glass (77, 111). The spectrum at room temperature, obtained only in the vCH region, showed absorptions at 3015, 2970, ca. 2930, and ca. 2880 cm 1 (Fig. 5D). These denote the... 

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