Clusters vaporization method

Application of other synthetic techniques, predominantly metal vapor methods, have added other cluster stoichiometries to this list, which presently includes Au5, Au , Aug, Aug, and Aun. The few examples for Au2 (3, 69), Au3 (30), and Am (36, 76) will not be considered here, since they do not involve gold in unusual oxidation states. The sections are ordered according to the cluster size, although, historically, the Aun moiety was the first to be detected (65). 

A second very important point when discussing effects of particle size is the distribution in size of the clusters. The latter is generally wide in real catalysts due to the methods of preparation vide infra). The observed rate is thus an average of the behavior of each entity of the population. Methods for the preparation of model supported catalysts, with very narrow particle-size distribution, are now developed and proceed through cluster vapor deposition [27]. Even in this case, the behavior of an individual particle is not always simple to interpret because the rate is not simply the average between the intrinsic rates on the different facets of the cluster. In fact, the facets are connected through edges that can accelerate the rate, or the reverse. 

Figure 9.2 Apparatus for preparation of metal clusters in zeolites through vapor method. Reproduced from [4], Copyright (2002) Springer-Verlag...

At the same time cis Smalley and students at Rice University, Houston Texas, developed the laser vaporization method for production of clusters [84], a similar set-up was built at Exxon s Research Laboratory, New Jersey, USA, by the group of Kaldor and Cox [102,103]. They studied in particular transition metal clusters but also produced clusters of carbon containing up to more than hundreds of atoms as shown in the mass spectrum in Fig. 12. 

A method has recently been described for wrapping polymers around metal atoms and very small metal clusters using both matrix and macroscale metal vapor-fluid polymer synthetic techniques. Significant early observations are that (i) the experiments can be entirely conducted at, or close to room temperature, (ii) the resulting "pol5aner stabilized metal cluster combinations are homogeneous liquids which are stable at or near room temperature, and (,iii) the methodology is easily extended to bimetallic and trimetallic polymer combinations. ... 

Silver vapor cocondensed with matrices of HjO or paraffin wax (C22H4 ) at 12 K gives mainly an atomic dispersion of Ag. However when these Ag atom matrices are warmed briefly (to 77 K for HjO and up to 80 K for C22H46), thermal diffusion takes place with aggregation of the Ag atoms into small clusters of up to Ag4. These thermal aggregation methods can be used to prepare small clusters, but a mixture of metal polymers is usually obtained. 

These methods may be used to prepare mixed metal clusters. Simultaneous codeposition of Ag and Cu vapors in Ar at 10-12 K yields a mixture including atomic Ag and Cu, dimers Ag, and Cu, together with AgCu. At 77 K, CuAg4 and Cu,Ag3 clusters occur . The amount of AgCu can be increased by photoexcitation with 305 nm Ag or Cu atomic radiation. The trimer AuAgCu is produced when a mixture of Au, Ag and Cu vapors is condensed at 77 K. 

There are several methods in use for producing these clusters. Particle bombardment or laser vaporization of a graphite surface leads to direct formation of ions that can be detected by mass spectrometry. These are normally of relatively small size (n<30). By laser vaporization of graphite into a molecular beam neutral... 

A review of preparative methods for metal sols (colloidal metal particles) suspended in solution is given. The problems involved with the preparation and stabilization of non-aqueous metal colloidal particles are noted. A new method is described for preparing non-aqueous metal sols based on the clustering of solvated metal atoms (from metal vaporization) in cold organic solvents. Gold-acetone colloidal solutions are discussed in detail, especially their preparation, control of particle size (2-9 nm), electrophoresis measurements, electron microscopy, GC-MS, resistivity, and related studies. Particle stabilization involves both electrostatic and steric mechanisms and these are discussed in comparison with aqueous systems. 

A variation on this method, passing the vapors emitted from a heated source or sources through a nozzle, may cause clustering. The gas-phase species, which could be ions or neutral molecules, pass from a region of higher pressure to a region of lower pressure. This process has many collisions and then adiabatic expansion often produces cold clusters. If the clusters have not been ionized, they may be ionized in the low-vacuum region. 

There are several preparative methods for the production of bare metal clusters including the fast flow reactor (PER), the fast flow tube reactor (FTR), the SIDT (24), the GIB (23), and a supersonic cluster beam source (SCBS) (198). Essentially, all of these methods are similar. The first process is to vaporize the metal sample producing atoms, clusters, and ions. Laser vaporization is generally favored although FAB or FIB may be used. The sample is located in a chamber or a tube and so vaporization generally takes place in a confined environment. An inert gas such as helium may be present in the vaporization source or may be pulsed in after the ionization process. 

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