Small metal particles

These questions lead on to further fundamental questions concerning the shapes and properties of small metal particles. For example, what is the stable shape for a small metal particle How is this affected by size, method of preparation, temperature, gaseous environment, precursor compound, support morphology, etc. Do small metal particles have different electronic properties from bulk metal Do surface electronic properties depend on particle size, and if so, do they vary in the same way as bulk electronic properties When, indeed, is a particle small enough to have unusual properties  

To answer these questions requires some understanding of the properties of small metal particles, both structural and electronic. In this review we shall examine first the evidence relating to metal particles prepared by direct methods, e.g., vapour deposition or condensation in the gas phase. Then we shall consider whether this information can be applied to the case of supported metals where both precursor decomposition and support effects may add to the complexity of the total system. We shall then consider whether further changes in catalytic properties occur after preparation, i.e., during the catalytic reaction. Finally, we shall summarize some of the more recent evidence concerning the nature of structure sensitivity. 

What is meant by the term small In terms of structure, small can mean the size below which the proportion of surface atoms having a particular coordination number begins to change rapidly with particle dimensions. In terms of electronic properties small can mean the size at which a particle begins to exhibit electronic properties which are not typical of a bulk metal. 

Operational Definition of Small as a Structural Parameter — Co-ordination 

van Hardeveld and F. Hartog, Proc. 4th Int. Congress on Catalysis, Moscow, 1968, paper 70. 

The above remarks are couched in very general terms, and apply to some extent to most forms of small metal particle. The available forms are (i) powders, a term which embraces a set of particles of any size, as long as it flows freely (Section 2.2), (ii) aerosols, (iii) colloidal dispersions (Section 2.2), and (iv) supported metals (Section 2.3), including particles formed by condensation of metal atoms onto a flat surface this leads ultimately to a condensed metal film. 

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The saturation coverage during chemisorption on a clean transition-metal surface is controlled by the fonnation of a chemical bond at a specific site [5] and not necessarily by the area of the molecule. In addition, in this case, the heat of chemisorption of the first monolayer is substantially higher than for the second and subsequent layers where adsorption is via weaker van der Waals interactions. Chemisorption is often usefLil for measuring the area of a specific component of a multi-component surface, for example, the area of small metal particles adsorbed onto a high-surface-area support [6], but not for measuring the total area of the sample. Surface areas measured using this method are specific to the molecule that chemisorbs on the surface. Carbon monoxide titration is therefore often used to define the number of sites available on a supported metal catalyst. In order to measure the total surface area, adsorbates must be selected that interact relatively weakly with the substrate so that the area occupied by each adsorbent is dominated by intennolecular interactions and the area occupied by each molecule is approximately defined by van der Waals radii. This... 

Krelbig U and Genzel L 1985 Optical absorption of small metallic particles Surf. Sol. 156 678... 

The finer soil fraction contains adsorbed organics, small metallic particles, and bound ionic metals. This fraction may be treated further to remove the contaminants, or it may be incinerated or landfilled. The "clean" coarse fraction may contain some residual metallic fragments. With metal contamination, both the fine and coarse soil fractions may be leached with an acid solution to remove the metals. 

There are only a few weU-documented examples of catalysis by metal clusters, and not many are to be expected as most metal clusters are fragile and fragment to give metal complexes or aggregate to give metal under reaction conditions (39). However, the metal carbonyl clusters are conceptually important because they form a bridge between catalysts commonly used in solution, ie, transition-metal complexes with single metal atoms, and catalysts commonly used on surfaces, ie, small metal particles or clusters. 

Let us consider small metallic particles with complex dielectric function e /jfco) embedded in an insulating host with complex dielectric function e/fco) as shown in Fig. 6. The ensemble, particles and host, have an effective dielectric function = e j i(co) -I- We can express the electric field E at any point... 

Fig. 10. In the first step few small metallic particles are dispersed in an insulating host. This modifies the medium which now has a dielectric function e,jy(0)) instead of e,(M). We repeat iteratively this process (in n consecutive steps) of adding metallic particles until we reach a filling/.

The Characterization and Properties of Small Metal Particles. Y. Takasu and A. M. Bradshaw, Surf. Defect. Prop. Solids p. 401 1978). 2. Cluster Model Theory. R. P. Messmer, in "The Nature of the Chemisorption Bond G. Ertl and T. Rhodin, eds. North-Holland Publ., Amsterdam, 1978. 3. Clusters and Surfaces. E. L. Muetterties, T. N. Rhodin, E. Band, C. F. Brucker, and W. R. Pretzer, Cornell National Science Center, Ithaca, New York, 1978. 4. Determination of the Properties of Single Atom and Multiple Atom Clusters. J. F. Hamilton, in "Chemical Experimentation Under Extreme Conditions (B. W. Rossiter, ed.) (Series, "Physical Methods of Organic Chemistry ), Wiley (Interscience), New York (1978). 

Diffraction patterns having relatively well-defined sharp spots can be obtained from small unit-cell crystals with an incident beam of diameter 10-158. Such patterns have been used in the study of the structures of small metal particles (22). For particles 10-20A diameter the electron beam can illuminate the whole of the particle... 

It Is not necessarily to be concluded that. In general, the proportion of small metal particles having the multiplicity twinned form decreases as the size Is decreased. The evidence concerning particles formed in other ways shows a great deal of variability. 

No hydride forms for very small particles. Yet when catalysts with such a small metal particle size are stored in air, they are converted to (crystalline) PdO. Reduction of this oxide with hydrogen produces Pd metal, not hydride. 

Small Metal Particles and Single Metal Atoms. 120... 

We have reviewed experiments on two classes of systems, namely small metal particles and atoms on oxide surfaces, and Ziegler-Natta model catalysts. We have shown that metal carbonyls prepared in situ by reaction of deposited metal atoms with CO from the gas phase are suitable probes for the environment of the adsorbed metal atoms and thus for the properties of the nucleation site. In addition, examples of the distinct chemical and physical properties of low coordinated metal atoms as compared to regular metal adsorption sites were demonstrated. For the Ziegler-Natta model catalysts it was demonstrated how combination of different surface science methods can help to gain insight into a variety of microscopic properties of surface sites involved in the polymerization reaction. 

The shape of the nanoparticles depends on numerous parameters such as the nature of the metal and the support, the metal loading. Of the various models of polyhedral metal particles [106], the cubooctaedral structure can be used to represent small metallic particles (Scheme 31). Note that these idealized structures can vary with the nature of chemisorbed species (vide infra) and very subtle atomic rearrangements probably occur during catalytic events. 

Consider in more detail the phenomena occurring at the interface between the solution and a small metallic particle involved in electrophoresis. Upon contact with the electrolyte solution, the metal acquires a certain value of electrode potential E,... 

Application of small metal particles has attracted the attention of the scientists for a long time. As early as in the seventies Turkevich already prepared mono-dispersed gold particles [19], and later, using molecular transition metal carbonyl clusters [20], the importance of small nanoparticles increased considerably. One of the crucial points is whether turnover frequency measured for a given catalytic reaction increases or decreases as the particle size is diminished. 

The small metal particle size, large available surface area and homogeneous dispersion of the metal nanoclusters on the supports are key factors in improving the electrocatalytic activity and the anti-polarization ability of the Pt-based catalysts for fuel cells. The alkaline EG synthesis method proved to be of universal significance for preparing different electrocatalysts of supported metal and alloy nanoparticles with high metal loadings and excellent cell performances. 

Horanyi G. 1985. Comments on the electrochemical behavior of small metal particles. J Phys Chem 89 2967-2968. 

Common to all encapsulation methods is the provision for the passage of reagents and products through or past the walls of the compartment. In zeolites and mesoporous materials, this is enabled by their open porous structure. It is not surprising, then, that porous silica has been used as a material for encapsulation processes, which has already been seen in LbL methods [43], Moreover, ship-in-a-bottle approaches have been well documented, whereby the encapsulation of individual molecules, molecular clusters, and small metal particles is achieved within zeolites [67]. There is a wealth of literature on the immobilization of catalysts on silica or other inorganic materials [68-72], but this is beyond the scope of this chapter. However, these methods potentially provide another method to avoid a situation where one catalyst interferes with another, or to allow the use of a catalyst in a system limited by the reaction conditions. For example, the increased stability of a catalyst may allow a reaction to run at a desired higher temperature, or allow for the use of an otherwise insoluble catalyst [73]. 

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