Supported metals metal distribution

In the case of metal particles distributed on a support material (e.g. supported catalysts), XPS yields infomiation on the dispersion. A higher metal/support intensity ratio (at the same metal content) indicates a better dispersion [3]. 

Supports. The principal component of a typical catalyst is the porous support (49,50). Most supports are robust soHds that can be made with wide ranges of surface areas and pore size distributions. The most widely appHed supports are metal oxides others are carbon, kieselguhr, organic polymers, and zeoHtes. 

In addition to obtaining Information about the size, relative mass, and structure of the platinum crystallites, the STEM can provide a qualitative evaluation of the metal distribution from support particle to support particle. In general, the distribution of platinum was more uniform on alumina than silica, however, optimal uniformity was not achieved. This observation was based on wide variations In Pt/Sl and Pt/Al ratios measured by EDS. 

The identification of structure sensitivity would be both impossible and useless if there did not exist reproducible recipes able to generate metal nanoparticles on a small scale and under controlled conditions, that is, with narrow size and/or shape distribution onto supports. Metal nanoparticles of controlled size, shape, and structure are attractive not only for catalytic applications, but are important, for example in optics, data storage, or electronics (c.f. Chapter 5). In order not to anticipate other chapters of this book (esp. Chapter 2), remarks will therefore be confined to few examples. 

Figure 6. Schematic representation of the micro- and nanoscale morphology of nanoclustered metal catalysts supported on gel-type (a) and macroreticular (b) resins [13]. The nanoclusters are represented as black spots. Level 1 is the representation of the dry materials. Level 2 is the representation of the microporous swollen materials at the same linear scale swelling involves the whole mass of the catalyst supported on the gel-type resin (2a) and the macropore walls in the catalyst supported on macroreticular resin (2b). The metal nanoclusters can be dispersed only in the swollen fractions of the supports, hence their distribution throughout the polymeric mass can be homogeneous in the gel-type supports, but not in the macroreticular ones (3a,b). In both cases, the metal nanoclusters are entangled into the polymeric framework and their nano-environment is similar in both cases, as shown in level 4.

The observed distribution can be readily explained upon assuming that the only part of polymer framework accessible to the metal precursor was the layer of swollen polymer beneath the pore surface. UCP 118 was meta-lated with a solution of [Pd(AcO)2] in THF/water (2/1) and palladium(II) was subsequently reduced with a solution of NaBH4 in ethanol. In the chemisorption experiment, saturation of the metal surface was achieved at a CO/Pd molar ratio as low as 0.02. For sake of comparison, a Pd/Si02 material (1.2% w/w) was exposed to CO under the same conditions and saturation was achieved at a CO/Pd molar ratio around 0.5. These observations clearly demonstrate that whereas palladium(II) is accessible to the reactant under solid-liquid conditions, when a swollen polymer layer forms beneath the pore surface, this is not true for palladium metal under gas-solid conditions, when swelling of the pore walls does not occur. In spite of this, it was reported that the treatment of dry resins containing immobilized metal precursors [92,85] with dihydrogen gas is an effective way to produce pol-5mer-supported metal nanoclusters. This could be the consequence of the small size of H2 molecules, which... 

Ir catalysts supported on binary oxides of Ti/Si and Nb/Si were prepared and essayed for the hydrogenation of a,P-unsaturated aldehydes reactions. The results of characterization revealed that monolayers of Ti/Si and Nb/Si allow a high metal distribution with a small size crystallite of Ir. The activity test indicates that the catalytic activity of these solids is dependent on the dispersion obtained and acidity of the solids. For molecules with a ring plane such as furfural and ciimamaldehyde, the adsorption mode can iirfluence the obtained products. SMSI effect (evidenced for H2 chemisorption) favors the formation of unsaturated alcohol. 

Particle size distribution for supported metals sometimes measured from electron micrographs and sometimes calculated from the measured number of... 

The mercury penetration approach is based on the fact that liquid mercury has a very high surface tension and the observation that mercury does not wet most catalyst surfaces. This situation holds true for oxide catalysts and supported metal catalysts that make up by far the overwhelming majority of the porous commercial materials of interest. Since mercury does not wet such surfaces, the pressure required to force mercury into the pores will depend on the pore radius. This provides a basis for measuring pore size distributions through measurements of the... 

In the last few years remarkable progress has been made in the preparation of supported metal catalysts. Entirely new methods have been developed, comprising precipitation of the metal as an insoluble salt or hydroxide on the support under controlled conditions, or loading the support with the metal by means of ion exchange. A feature of catalysts prepared according to the former method (I, 2) is that, after reduction, they have a high metal content (50% by weight, or more), while the metal crystals are still small (20-40 A) and distributed very uniformly over the support. The latter approach yields catalysts with metal crystallites of approximately 10 A however, the metal content is rather low [about 2% (3-5)]. 

In many catalytic systems, nanoscopic metallic particles are dispersed on ceramic supports and exhibit different stmctures and properties from bulk due to size effect and metal support interaction etc. For very small metal particles, particle size may influence both geometric and electronic structures. For example, gold particles may undergo a metal-semiconductor transition at the size of about 3.5 nm and become active in CO oxidation [10]. Lattice contractions have been observed in metals such as Pt and Pd, when the particle size is smaller than 2-3 nm [11, 12]. Metal support interaction may have drastic effects on the chemisorptive properties of the metal phase [13-15]. Therefore the stmctural features such as particles size and shape, surface stmcture and configuration of metal-substrate interface are of great importance since these features influence the electronic stmctures and hence the catalytic activities. Particle shapes and size distributions of supported metal catalysts were extensively studied by TEM [16-19]. Surface stmctures such as facets and steps were observed by high-resolution surface profile imaging [20-23]. Metal support interaction and other behaviours under various environments were discussed at atomic scale based on the relevant stmctural information accessible by means of TEM [24-29]. 

Figure 2.15 Schematic representation of the silica supported metallic particle with a cubo-octahedral shape (a) and a real particle size distribution of platinum nanoclusters supported on silica (b).

The severe working conditions often encountered in an H2 production process, such as high temperature and high space velocity, combined with the necessity for a long catalyst lifetime, impose the development of an appropriate synthetic procedure to stabilize the catalyst. The reforming activity and product distribution over supported metal catalysts depend on the choice of metal and its content, the presence of promoters, the type of support and method of catalyst preparation. 

Raman spectra of adsorbed species, when obtainable, are of great importance because of the very different intensity distributions among the observable modes (e.g., the skeletal breathing frequency of benzene) compared with those observed by infrared spectroscopy and because Raman spectra of species on oxide-supported metals have a much wider metal oxide-transparent wavenumber range than infrared spectra. Such unenhanced spectra remain extremely weak for species on single-crystal surfaces, but renewed efforts should be made with finely divided catalysts, possibly involving pulsed-laser operation to minimize adsorbate decomposition. Renewed efforts should be made to obtain SER and normal Raman spectra characterizing adsorption on surfaces of the transition metals such as Ni, Pd, or Pt, by use of controlled particle sizes or UV excitation, respectively. 

Among the early systemmatic studies of the metal-catalysed hydrogenation of acetylene were those of Sheridan et al. [158,168—170] who investigated the kinetics and product distributions over pumice-supported metals. Subsequently, the reaction has been extensively studied by Bond et al. [9,165,171—175] over pumice- and alumina-supported metals and metal powders. The reaction of acetylene with deuterium over nickel [91, 163] and alumina-supported noble Group VIII metals [164,165] has also been investigated. 

Typical deuterobutene distributions observed in the reaction but-2-yne with deuterium over alumina-supported metals... 

Deuterobutene distributions observed in the reaction of buta-1 3-diene with deuterium ovei alumina-supported metals [166,167]... 

Initial distributions of products observed in the hydrogenation of penta-1 3-diene over various alumina-supported metals [215]... 

For supported-metal catalysts, the questions of interaction with and location of the metal on the support are of important concern, since these factors may be instrumental in determining, for example, the metal particle size and size distribution, the particle size stability to thermal and chemical treatments, and the accessibility of the metal to the reactants of the catalytic process. That these questions are amenable to study using the Mbssbauer effect is the topic of this section. 

Aspects of the distribution of species on surfaces have been reviewed (35) and our understanding of the disposition, composition, and properties of the adsorbed phase is increasing through applications of recently developed high-vacuum techniques, for example, LEED (60, 61). Some information about the mobility of adsorbed material is available (62a-e) and the significance of surface diffusivity in reaction kinetics has been discussed (63). The behavior of supported metal catalysts may be influenced by the transfer of material between the two phases (metal and support) by diffusion (64-66). 

The performance of a catalyst is well known to be sensitive to its preparation procedure. For this reason, ideally an oxide-supported metal catalyst should be subjected to a number of characterization procedures. These may include measurements of the metal loading within the overall catalyst (usually expressed in wt%), the degree of metal dispersion (the proportion of metal atoms in the particle surfaces), the mean value and the distribution of metal particle diameters, and qualitative assessments of morphology including the particle shapes and evidence for crystallinity. These properties in turn can depend on experimental variables used in the preparation, such as the choice and amounts of originating metal salts, prereduction, calcination or oxygen treatments, and the temperature and duration of hydrogen reduction procedures. 

Another spectrum from a n complex has been observed by SERS following the adsorption of propene on cold-evaporated Ag (229). The intensity distribution, as expected for a Raman spectrum, is different from that in the infrared spectrum, but it does show readily observed features at 1612 and 1300 cm-1 from the coupled vC=C and <5=CH2 modes (1557 and 1267 cm-1 on Cu). As the corresponding absorptions on Pt or Ni are expected to be at notably lower wavenumbers than on Cu or Ag, and as no absorptions are discernible between 1550 and 1460 cm-1 in the spectra on the group VIII metal surfaces, this negative result reinforces the view that n species are not abundant on the latter catalysts. A recent theoretical study by Delbecq and Sautet (252) has, in agreement, concluded that for propene on Pt(lll) the n species is less stable with respect to di-cr than is the case for ethene on Pd(l 11) the difference was much less marked. More low- and room-temperature studies of propene on several Al203-supported metals are needed to obtain reliable information about the nonpropylidyne species. 

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