Metal dispersed

Clusters are intennediates bridging the properties of the atoms and the bulk. They can be viewed as novel molecules, but different from ordinary molecules, in that they can have various compositions and multiple shapes. Bare clusters are usually quite reactive and unstable against aggregation and have to be studied in vacuum or inert matrices. Interest in clusters comes from a wide range of fields. Clusters are used as models to investigate surface and bulk properties [2]. Since most catalysts are dispersed metal particles [3], isolated clusters provide ideal systems to understand catalytic mechanisms. The versatility of their shapes and compositions make clusters novel molecular systems to extend our concept of chemical bonding, stmcture and dynamics. Stable clusters or passivated clusters can be used as building blocks for new materials or new electronic devices [4] and this aspect has now led to a whole new direction of research into nanoparticles and quantum dots (see chapter C2.17). As the size of electronic devices approaches ever smaller dimensions [5], the new chemical and physical properties of clusters will be relevant to the future of the electronics industry. 

Catalytic Properties. In zeoHtes, catalysis takes place preferentially within the intracrystaUine voids. Catalytic reactions are affected by aperture size and type of channel system, through which reactants and products must diffuse. Modification techniques include ion exchange, variation of Si/A1 ratio, hydrothermal dealumination or stabilization, which produces Lewis acidity, introduction of acidic groups such as bridging Si(OH)Al, which impart Briimsted acidity, and introducing dispersed metal phases such as noble metals. In addition, the zeoHte framework stmcture determines shape-selective effects. Several types have been demonstrated including reactant selectivity, product selectivity, and restricted transition-state selectivity (28). Nonshape-selective surface activity is observed on very small crystals, and it may be desirable to poison these sites selectively, eg, with bulky heterocycHc compounds unable to penetrate the channel apertures, or by surface sdation. 

Dispersed Metals. Bifimctional zeoHte catalysts, principally zeoHte Y, are used in commercial processes such as hydrocracking. These are acidic zeoHtes containing dispersed metals such as platinum or palladium. The metals are introduced by cation exchange of the ammine complexes, foUowed by a reductive decomposition (21) ... 

In particular, emphasis will be placed on the use of chemisorption to measure the metal dispersion, metal area, or particle size of catalytically active metals supported on nonreducible oxides such as the refractory oxides, silica, alumina, silica-alumina, and zeolites. In contrast to physical adsorption, there are no complete books devoted to this aspect of catalyst characterization however, there is a chapter in Anderson that discusses the subject. 

With special techniques for the activation of the metal—e.g. for removal of the oxide layer, and the preparation of finely dispersed metal—the scope of the Refor-matsky reaction has been broadened, and yields have been markedly improved." The attempted activation of zinc by treatment with iodine or dibromomethane, or washing with dilute hydrochloric acid prior to use, often is only moderately successful. Much more effective is the use of special alloys—e.g. zinc-copper couple, or the reduction of zinc halides using potassium (the so-called Rieke procedure ) or potassium graphite. The application of ultrasound has also been reported. ... 

Consequently the absolute potential is a material property which can be used to characterize solid electrolyte materials, several of which, as discussed in Chapter 11, are used increasingly in recent years as high surface area catalyst supports. This in turn implies that the Fermi level of dispersed metal catalysts supported on such carriers will be pinned to the Fermi level (or absolute potential) of the carrier (support). As discussed in Chapter 11 this is intimately related to the effect of metal-support interactions, which is of central importance in heterogeneous catalysis. 

In dispersed metal-support systems (Fig. 11.2 right), one can vary pe(M) - M-e(S) by varying the support or by doping the support with aliovalent cations. This is known in the literature as dopant-induced metal-support interactions (DIMSI).8,11,41,42 Thus one can again vary the electrochemical potential and thus the coverage of backspillover O2 on the supported catalyst surface. 

A major obstacle is related to the anode material. The active component in the anode is a highly dispersed metal supported on graphite that is pressed against the membrane. Platinum is chosen as the active metal because of its efficiency in dissociating hydrogen, but, unfortunately, platinum is also very sensitive towards trace amounts of impurities (e.g. CO) in the hydrogen gas. 

Investigations utilizing EXAFS have the very important feature of yielding information in an environment of the kind actually encountered in catalysis. We have recently demonstrated the feasibility of making measurements while a catalytic reaction is actually occurring. One can anticipate that measurements of this type will receive Increased emphasis in the future. For studies of the structures of highly dispersed metal catalysts, EXAFS may well be the most generally applicable physical probe currently available. 

The use of highly dispersed metals at low concentration levels has found wide use In Industry, particularly for electronic and catalytic uses. The desire to optimize the size and mass uniformity of these metal particles Is of particular Interest. Characterization of these materials Is difficult especially when metal particle sizes are on the order of 5 nm or less and concentrations are below 1 wt-Z. Development of highly sophisticated techniques In recent years has provided new approaches to understanding the physical and chemical properties of these materials. Electron microscopy has proven quite valuable In the acquisition of data and subsequent generation of information, which Is necessary to understand the physical-chemical properties of Individual nm-slzed particles. 

The STEM Is Ideally suited for the characterization of these materials, because one Is normally measuring high atomic number elements In low atomic number metal oxide matrices, thus facilitating favorable contrast effects for observation of dispersed metal crystallites due to diffraction and elastic scattering of electrons as a function of Z number. The ability to observe and measure areas 2 nm In size In real time makes analysis of many metal particles relatively rapid and convenient. As with all techniques, limitations are encountered. Information such as metal surface areas, oxidation states of elements, chemical reactivity, etc., are often desired. Consequently, additional Input from other characterization techniques should be sought to complement the STEM data. 

The dedicated STEM provides a means of obtaining mlcroanalytlcal Information of supported metals not readily obtained by other Instrumentation. The capability to observe and analyze some very highly dispersed metal particles on y-alumlna has been demonstrated and for the noble metals, verified by temperature prograouned hydrogen desorption. 

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]. 

It is first necessary to distinguish the surface organometallic chemistry on metals and on oxides since one deals with a large ensemble of metals, while the others generate dispersed metal atoms attached covalently onto the support. 

Most often, these disperse metal catalysts are supported by an electronically conducting substrate or carrier that should provide for uniform supply or withdrawal of electrons (current) to or from all catalyst crystallites. The substrate should also serve to stabilize the disperse state of the catalyst and retard any spontaneous coarsening of the catalyst crystallites. Two situations are to be distinguished (1) the disperse metal catalyst is applied to a substrate consisting of the same metal, and (2) it is applied to a chemically different substrate (a foreign substrate). Platinized platinum is a typical example of the former situation. 

Different ways exist to prepare eiectrodes with highiy disperse metal catalysts and lead to the corresponding electrode varieties. 

These highly disperse metal powders are very active chemically, and hence unstable they readily aggregate to coarser particles, and readily oxidize when in contact with air. Their stability rises significantly when they have been applied to a suitable substrate. 

Experience has shown that the specific or intrinsic catalytic activity of electrodes with disperse metal catalysts when referred to the true working surface area often remains below that of smooth (compact) electrodes consisting of the same metal. Of course, owing to the large increase in total working surface area, the overall reachon rate is larger, but as a rule it is not larger by the expected factor of y. 

In principle, it should be possible to obtain experimental valence band spectra of highly dispersed metals by photoemission. In practice, such spectra is difficult to obtain because very highly dispersed metals are usually obtained only on nonconductive supports and the resulting charging of the sample causes large chemical shifts and severe broadening of the photoelectron spectra. The purpose of this section is to discuss valence band and core level spectra of highly dispersed metal particles. 

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