Catalyst, general crystallites

Results of similar experiments by Gault and his co-workers (93) with a 10-wt % Pt/Al203 catalyst (mean crystallite size 150-200 A) required the assumption that several successive rearrangements took place in the adsorbed phase before desorption. A model was developed in which either a dehydrocy-clization-hydrogenolysis event or a methyl or ethyl shift involving a tertiary atom competed with desorption. By assuming that the isomeric hexanes had the same desorption probability (d) and the different bond-shift processes proceeded with the same chance (r), it was found possible to reproduce the observed initial product distributions with these two independent parameters. In general, values of d 0.5 and t = 0.10-0.20 fitted the results best. As an additional refinement, the ratio of the C2—C3 and C3—C4 bond scission probabilities for methylcyclo-pentane (0) was taken to be 3.3, rather than the statistical value of 2, to improve further the fit. 

An interesting intermediate between homogeneous and heterogeneous catalysts are the metal cluster catalysts. In many reactions that require several active centers of the catalyst, it is found that heterogeneous catalysts are active, while homogeneous catalysts give zero conversion. The reason is that crystallites on a metal surface exhibit several active centers, while conventional soluble catalysts generally contain only one metal center. 

By using carbon to disperse the platinum, a dramatic reduction in Pt loading has also been achieved over the last two decades the loadings are currently approximately 0.10 mg Pt cm" in the anode and approximately 0.50 mg Pt cm 2 in the cathode. The choice of carbon is important, as is the method of dispersing the platinum. The activity of the PI catalyst depends on the type of catalyst, its crystallite size, and specific surface area. Small crystallites and high siuface areas generally lead to high catalyst activity. 

In ecent years the utility of extended X-ray absorption fine structure UXAFS) as a probe for the study of catalysts has been clearly demonstrated (1-17). Measurements of EXAFS are particularly valuable for very highly dispersed catalysts. Supported metal systems, in which small metal clusters or crystallites are commonly dispersed on a refractory oxide such as alumina or silica, are good examples of such catalysts. The ratio of surface atoms to total atoms in the metal clusters is generally high and may even approach unity in some cases. 

A wide variety of solid materials are used in catalytic processes. Generally, the (surface) structure of metal and supported metal catalysts is relatively simple. For that reason, we will first focus on metal catalysts. Supported metal catalysts are produced in many forms. Often, their preparation involves impregnation or ion exchange, followed by calcination and reduction. Depending on the conditions quite different catalyst systems are produced. When crystalline sizes are not very small, typically > 5 nm, the metal crystals behave like bulk crystals with similar crystal faces. However, in catalysis smaller particles are often used. They are referred to as crystallites , aggregates , or clusters . When the dimensions are not known we will refer to them as particles . In principle, the structure of oxidic catalysts is more complex than that of metal catalysts. The surface often contains different types of active sites a combination of acid and basic sites on one catalyst is quite common. 

Syndiotactic polypropylene became commercially available about ten years ago with the advent of single-site catalysts. Unlike its atactic and isotactic counterparts, its manufacture presented serious challenges to polymer scientists and engineers. Even under the best conditions, its syndiotacticity rarely exceeds 75%, based on pentad sequences. It typically has both a lower melting point (approximately 138 °C relative to approximately 155 to 160 °C) and density (0.89 g/cm3 relative to 0.93 g/cm3) than isotactic polypropylene. Syndiotactic polypropylene crystallites have a much more complex structure than the isotactic form, which impedes its crystallization. Therefore, in general, the syndiotactic form of polypropylene crystallizes very slowly. 

X-Ray studies confirm that platinum crystallites exist on carbon supports at least down to a metal content of about 0.03% (2). On the other hand, it has been claimed that nickel crystallites do not exist in nickel/carbon catalysts (50). This requires verification, but it does draw attention to the fact that carbon is not inert toward many metals which can form carbides or intercalation compounds with graphite. In general, it is only with the noble group VIII metals that one can feel reasonably confident that a substantial amount of the metal will be retained on the carbon surface in its elemental form. Judging from Moss s (35) electron micrographs of a reduced 5% platinum charcoal catalyst, the platinum crystallites appear to be at least as finely dispersed on charcoal as on silica or alumina, or possibly more so, but both platinum and palladium (51) supported on carbon appear to be very sensitive to sintering. 

Carrier The metal catalyst is generally dispersed on a high surface area carrier, ie, the carrier is given a washcoat of catalyst, such that very small (2—3 nm dia) precious metal crystallites are widely dispersed over the surface area, serving two basic functions. It maximizes the use of the cosdy precious metal, and provides a large surface area thereby increasing gas contact and associated catalytic reactions (18). 

Thermally induced deactivation of catalysts is a particularly difficult problem in high-temperature catalytic reactions. Thermal deactivation may result from one or a combination of the following (i) loss of catalytic surface area due to crystallite growth of the catalytic phase, (ii) loss of support area due to support collapse, (iii) reactions/transformations of catalytic phases to noncatalytic phases, and/or (iv) loss of active material by vaporization or volatilization. The first two processes are typically referred to as "sintering." Sintering, solid-state reactions, and vaporization processes generally take place at high reaction temperatures (e.g. > 500°C), and their rates depend upon temperature, reaction atmosphere, and catalyst formulation. While one of these processes may dominate under specific conditions in specified catalyst systems, more often than not, they occur simultaneously and are coupled processes. 

Of course, the crystallites considered in supported metal catalysts are small in general, of a size on the order of a few hundred angstroms. While the above considerations have been formulated having large droplets in mind, they can be extended at least from a qualitative point of view to the small crystallites. 

In eq 9, which is valid for thick films, It denotes the film thickness. Note that rm becomes very large for cos 0 = 1 (wetting situation), suggesting that the film is always favored relative to crystallite formation. For situations relevant to supported catalysts, the loading of the support by active phase would generally be small and, hence, the films would be thin. In this case, rm becomes dependent on a parameter a, which is pro-... 

Hall, Dieter, Hofer, and Anderson (19) studied reactions of nitrides and carbonitrides in a reduced, fused iron catalyst (Bureau of Mines number D3001). The results of these experiments were in general similar to those of Jack, and most of the differences may be explained by the differences in the type of iron employed. The major discrepancy was that in the catalyst of large surface area and small crystallite size, the <-carbonitride phase was found under conditions under which massive iron is converted to the f-phase. Since the transformation of the - to the f-phase involves only slight changes in the lattice positions of iron atoms and small changes in the x-ray pattern, it is possible either that this transformation did not occur in the catalyst or that the pattern of the f-phase could not be distinguished from that of the e-phase in the diffuse diffraction patterns. 

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