Metal Particles on Oxides

There are other fields where supported metal clusters will play a role like in the microelectronic technologies and in particular in the production of sensors or magnetic recording. Magnetic clusters provide a link between the magnetism at the atomic level and in the condensed state [25]. Finally, cluster-assembled materials offer new opportunities in material science. 

No matter which is the application, in order to be of practical use, the clusters must be deposited and stabilized on a substrate. This leads us to the second aspect of the problem namely that of the atomistic characterization of the supporting material and the defects present on its surface. 

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In the following review we will focus on two classes of systems dispersed metal particles on oxide supports as used for a large variety of catalytic reactions and a model Ziegler-Natta catalyst for low pressure olefin polymerization. The discussion of the first system will focus on the characterization of the environment of deposited metal atoms. To this end, we will discuss the prospects of metal carbonyls, which may be formed during the reaction of metal deposits with a CO gas phase, as probes for mapping the environment of deposited metal atoms [15-19]. 

From catalysis it is well-known that the metal-substrate interaction influences the reactivity of supported nanoparticles. For instance, for noble metal particles on oxidic supports, the hydrogenation and hydrogenolysis activity is much greater if the support has a higher acidity (high concentration of acidic —OH groups at the surface) than for neutral or alkaline oxidic supports. The influence of the presence of a support on the catalytic activity of metal nanoparticles has been ascribed to [70, 75-79] ... 

SCHWANK ET AL. Noble Metal Particles on Oxide Materials... 

The type of bond between the surface of the solid and adsorbate molecules determines the kind of surface processes that can take place crystal growth, growth inhibition, nucleation, corrosion, catalytic activity, and chemical passivation. Sometimes there are two types of surfaces involved in the reaction metallic and ionic (many heterogeneous catalysts consist of very small metal particles on oxidic carriers). 

The Beckstead-Derr-Price model (Fig. 1) considers both the gas-phase and condensed-phase reactions. It assumes heat release from the condensed phase, an oxidizer flame, a primary diffusion flame between the fuel and oxidizer decomposition products, and a final diffusion flame between the fuel decomposition products and the products of the oxidizer flame. Examination of the physical phenomena reveals an irregular surface on top of the unheated bulk of the propellant that consists of the binder undergoing pyrolysis, decomposing oxidizer particles, and an agglomeration of metallic particles. The oxidizer and fuel decomposition products mix and react exothermically in the three-dimensional zone above the surface for a distance that depends on the propellant composition, its microstmcture, and the ambient pressure and gas velocity. If aluminum is present, additional heat is subsequently produced at a comparatively large distance from the surface. Only small aluminum particles ignite and bum close enough to the surface to influence the propellant bum rate. The temperature of the surface is ca 500 to 1000°C compared to ca 300°C for double-base propellants. 

Figure 7. Electron energy loss spectroscopy (EELS) of a Cu/ZnO catalyst a) bright-field STEM image showing a 20nm copper oxide particle and a small 2nm Cu metal particle on ZnO, b) and c)...

As we have seen in the previous chapter, the apparent topography and corrugation of thin oxide films as imaged by STM may vary drastically as a function of the sample bias. This will of course play an important role in the determination of cluster sizes with STM, which will be discussed in the following section. The determination of the size of the metallic nanoparticles on oxide films is a crucial issue in the investigation of model catalysts since the reactivity of the particles may be closely related to their size. Therefore, the investigation of reactions on model catalysts calls for a precise determination of the particle size. If the sizes of the metal particles on an oxidic support are measured by STM, two different effects, which distort the size measurement, have to be taken into account. 

Practical metal catalysts frequently consist of small metal particles on an oxide support. Suitable model systems can be prepared by growing small metal aggregates onto single crystal oxide films, a technique whereby the role of the particle size or of the support material may be studied. [37] A quite remarkable example of the variation of the catalytic activity with particle size has recently been found for finely dispersed Au on a Ti02 support, which was revealed to be highly reactive for combustion reactions. [38] On the basis of STM experiments it was concluded that this phenomenon has to be attributed to a quantum size effect determined by the thickness of the gold layers. 

C. T. Campbell, Ultrathin metal films and particles on oxide surfaces Structural, electronic and chemisorptive properties, Surf. Sci. Rep. 27(1-3), 1-111 (1997). 

Figure 3. Hydrogenation catalyst with nm-size metallic particles on an oxide carrier (inverted STEM dark field image)...

The heat produced by the reaction of a pyrolant is dependent on various physicochemical properties, such as the chemical nature of the fuel and oxidizer, the fractions in which they are mixed, and their physical shapes and sizes. Metal particles are commonly used as fuel components of pyrolants. When a metal particle is oxidized by gaseous oxidizer fragments, an oxide layer is formed that coats the particle. If the melting point of the oxide layer is higher than that of the metal particle, the metal oxide layer prevents further supply of the oxidizer fragments to the metal, and so the oxidation remains incomplete. If, however, the melting point of the oxide layer is lower than that of the metal particle, the oxide layer is easily removed and the oxidation reaction can continue. 

In the case of oxide catalysts or alkali metal-doped oxide catalysts, basic surface sites can be generated by decarboxylation of a surface metal carbonate exchange of hydroxyl hydrogen ions by electropositive cations thermal dehydroxylation of the catalyst surface condensation of alkali metal particles on the surface and reaction of an alkali metal with an anion vacancy (AV) to give centers (e.g., Na + AV — Na + e ). 

Pfefferle and Lyubovsky executed types of measurements that yielded critical information between active Pd phases for catalytic combustion using pure ot-alumina plates with zero porosity as a support for the catalyst. This procedure uniformly covers the plate with metal particles on the top surface where they are easily available for the reaction gases and optical analysis. This type of experimental procedure has shown that in high-temperature methane oxidation the reduced form of the supported palladium catalyst is more active than the oxidized form. The temperature at which the PdO Pd... 

Another way of investigating structure is through the classical method on metals of varying catalyst particle size. The key to this method is to measure active catalyst surface areas in order to determine changes in turnover rates with ensemble size. In recent years several chemisorption techniques have been developed to titrate surface metal centers on oxides (25). In this volume Rao and Narashimha and Reddy report on the use of oxygen chemisorption to characterize supported vanadium oxide. 

A variety of industrial catalytic processes employ small metal-particle catalysts on porous inorganic supports. The particle sizes are increasingly in the nanometre size range which gives rise to nanocatalysts. As described in chapter 1, commonly used supports are ceramic oxides, like alumina and silica, or carbon. Metal (or metallic) catalysts in catalytic technologies contain a high dispersion of nanoscopic metal particles on ceramic oxide or carbon supports. This is to maximize the surface area with a minimum amount of metal for catalytic reactions. It is desirable to have all of the metal exposed to reactants. 

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