Supported metals metal dispersions

Carbon number distributions are similar on all Co catalysts. As on Ru catalysts, termination probabilities decrease with increasing chain size, leading to non-Flory product distributions. The modest effects of support and dispersion on product molecular weight and C5+ selectivity (Table III) reflect differences in readsorption site density and in support pore structure (4,5,14,40,41), which control the contributions of olefin readsorption to chain growth. Carbon number distributions obey Flory kinetics for C30+ hydrocarbons the chain growth probability reaches a constant value (a ) as olefins disappear from the product stream. This constant value reflects the intrinsic probability of chain termination to paraffins by hydrogen addition it is independent of support and metal dispersion in the crystallite size range studied. 

Based on quantitative GPLE treatments of sintering kinetics, it is possible to define effects of metal, metal dispersion, metal concentration, and support thermal stability ... 

Palladium 5% on activated carbon Vm (Ncc/g support) Surface area (m /g metal) Metal dispersion (%)... 

In catalysis, oxides with well defined acidic and basic properties are used in different forms that have found application in numerous catalytic applications in the gas-solid and liquid-solid heterogeneous catalysis [3, 46, 47], Among the most used oxide materials in catalysis, we And (i) bulk oxides (one component metal oxides) (ii) doped and moditied oxides (iii) supported metal oxides (dispersed active oxide component onto a support oxide component) (iv) bulk and supported binary metal oxides to quaternary metal oxides (mixed oxide compositions) (v) complex oxides (e.g., spinels, perovskites, hexa-aluminates, bulk and supported hydrotalcites, pillared clays, bulk and supported heteropolyacids, layered silicas, etc.). 

A few industrial catalysts have simple compositions, but the typical catalyst is a complex composite made up of several components, illustrated schematically in Figure 9 by a catalyst for ethylene oxidation. Often it consists largely of a porous support or carrier, with the catalyticaHy active components dispersed on the support surface. For example, petroleum refining catalysts used for reforming of naphtha have about 1 wt% Pt and Re on the surface of a transition alumina such as y-Al203 that has a surface area of several hundred square meters per gram. The expensive metal is dispersed as minute particles or clusters so that a large fraction of the atoms are exposed at the surface and accessible to reactants (see Catalysts, supported). 

CatalyticaHy Active Species. The most common catalyticaHy active materials are metals, metal oxides, and metal sulfides. OccasionaHy, these are used in pure form examples are Raney nickel, used for fat hydrogenation, and y-Al O, used for ethanol dehydration. More often the catalyticaHy active component is highly dispersed on the surface of a support and may constitute no more than about 1% of the total catalyst. The main reason for dispersing the catalytic species is the expense. The expensive material must be accessible to reactants, and this requires that most of the catalytic material be present at a surface. This is possible only if the material is dispersed as minute particles, as smaH as 1 nm in diameter and even less. It is not practical to use minute... 

Supported metal catalysts are reduced, for example, by treatment in hydrogen at temperatures in the range of 300—500°C. The reduction temperature may influence the stabiUty of the metal dispersion. 

Cost. The catalytically active component(s) in many supported catalysts are expensive metals. By using a catalyst in which the active component is but a very small fraction of the weight of the total catalyst, lower costs can be achieved. As an example, hydrogenation of an aromatic nucleus requires the use of rhenium, rhodium, or mthenium. This can be accomplished with as fittie as 0.5 wt % of the metal finely dispersed on alumina or activated carbon. Furthermore, it is almost always easier to recover the metal from a spent supported catalyst bed than to attempt to separate a finely divided metal from a liquid product stream. If recovery is efficient, the actual cost of the catalyst is the time value of the cost of the metal less processing expenses, assuming a nondeclining market value for the metal. Precious metals used in catalytic processes are often leased. 

Precious Meta.1 Ca.ta.lysts, Precious metals are deposited throughout the TWC-activated coating layer. Rhodium plays an important role ia the reduction of NO, and is combiaed with platinum and/or palladium for the oxidation of HC and CO. Only a small amount of these expensive materials is used (31) (see Platinum-GROUP metals). The metals are dispersed on the high surface area particles as precious metal solutions, and then reduced to small metal crystals by various techniques. Catalytic reactions occur on the precious metal surfaces. Whereas metal within the crystal caimot directly participate ia the catalytic process, it can play a role when surface metal oxides are influenced through strong metal to support reactions (SMSI) (32,33). Some exhaust gas reactions, for instance the oxidation of alkanes, require larger Pt crystals than other reactions, such as the oxidation of CO (34). 

Base catalysis is most effective with alkali metals dispersed on solid supports or, in the homogeneous form, as aldoxides, amides, and so on. Small amounts of promoters form organoalkali comnpounds that really contribute the catalytic power. Basic ion exchange resins also are usebil. Base-catalyzed processes include isomerization and oligomerization of olefins, reactions of olefins with aromatics, and hydrogenation of polynuclear aromatics. 

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. 

As this field is very wide, we will discuss first the gases that can be used to study metal dispersion by selective chemisorption, and then some specific examples of their application. The choice of gases, is, of course, restricted to those that will strongly chemisorb on the metal, but will not physically adsorb on the support. Prior to determining the chemisorption isotherm, the metal must be reduced in flowing hydrogen details are given elsewhere. The isotherm measurement is identical to that used in physical adsorption. 

The use of CO is complicated by the fact that two forms of adsorption—linear and bridged—have been shown by infrared (IR) spectroscopy to occur on most metal surfaces. For both forms, the molecule usually remains intact (i.e., no dissociation occurs). In the linear form the carbon end is attached to one metal atom, while in the bridged form it is attached to two metal atoms. Hence, if independent IR studies on an identical catalyst, identically reduced, show that all of the CO is either in the linear or the bricked form, then the measurement of CO isotherms can be used to determine metal dispersions. A metal for which CO cannot be used is nickel, due to the rapid formation of nickel carbonyl on clean nickel surfaces. Although CO has a relatively low boiling point, at vet) low metal concentrations (e.g., 0.1% Rh) the amount of CO adsorbed on the support can be as much as 25% of that on the metal a procedure has been developed to accurately correct for this. Also, CO dissociates on some metal surfaces (e.g., W and Mo), on which the method cannot be used. 

As it was established by Geus et a/.[18, 19] the decrease of the rate of carbon deposition is a positive factor for the growth of fibres on metal catalysts. Si02 is an inhibitor of carbon condensation as was shown in Ref [20]. This support also provides possibilities for the stabilization of metal dispersion. Co and Fe, i.e. the metals that give the best results for the tubular condensation of carbon on graphite support, were introduced on the surface of siUca gel... 

The catalysts used in the process are essentially nickel metal dispersed on a support material consisting of various oxide mixtures such as alumina, silica, lime, magnesia, and compounds such as calcium aluminate cements. When the catalyst is made, the nickel is present as nickel oxide which is reduced in the plant converter with hydrogen, usually the 3 1 H2 N2 synthesis gas ... 

It will also be shown that the absolute electrode potential is not a property of the electrode but is a property of the electrolyte, aqueous or solid, and of the gaseous composition. It expresses the energy of solvation of an electron at the Fermi level of the electrolyte. As such it is a very important property of the electrolyte or mixed conductor. Since several solid electrolytes or mixed conductors based on ZrC>2, CeC>2 or TiC>2 are used as conventional catalyst supports in commercial dispersed catalysts, it follows that the concept of absolute potential is a very important one not only for further enhancing and quantifying our understanding of electrochemical promotion (NEMCA) but also for understanding the effect of metal-support interaction on commercial supported catalysts. 

This study, in conjunction with that discussed in 12.2.1.2, show that when using aqueous electrolytes or Nafion saturated with H20, the induction of NEMCA on finely dispersed noble metal catalysts is rather straightforward. The role of the electronically conducting porous C support is only to conduct electrons and to support the finely dispersed catalyst. The promoting species can reach the active catalyst via the electrolyte or via the aqueous film without having to migrate on the surface of the support, as is the case when using ceramic solid electrolytes. 

Bimolecular reactions are sometimes catalyzed using two different metals dispersed on a common support. A mechanism might be... 

Usually noble metal NPs highly dispersed on metal oxide supports are prepared by impregnation method. Metal oxide supports are suspended in the aqueous solution of nitrates or chlorides of the corresponding noble metals. After immersion for several hours to one day, water solvent is evaporated and dried overnight to obtain precursor (nitrates or chlorides) crystals fixed on the metal oxide support surfaces. Subsequently, the dried precursors are calcined in air to transform into noble metal oxides on the support surfaces. Finally, noble metal oxides are reduced in a stream containing hydrogen. This method is simple and reproducible in preparing supported noble metal catalysts. 

As can be seen in table 1, with different preparation methods and active metals, the average size of the copper particle for the catalysts A and D were 20.3 nm and 50.0 nm. While those of the catalysts B and C were 51.3 nm and 45.4 run, respectively. CuO, non-supported metal oxide, made by impregnation is sintered and cluster whose particle size was 30 pm. The water-alcohol method provided more dispersed catalysts than the impregnation method. 

Fig. 4 shows the current density over the supported catalysts measured in 1 M methanol containing 0.5 M sulfuric acid. During forward sweep, the methanol electro-oxidation started to occur at 0.35 V for all catalysts, which is typical feature for monometallic Pt catalyst in methanol electro-oxidation [8]. The maximum current density was decreased in the order of Pt/CMK-1 > Pt/CMK-3 > Pt/Vulcan. It should be noted that the trend of maximum current density was identical to that of metal dispersion (Fig. 2 and Fig. 3). Therefore, it is concluded that the metal dispersion is a critical factor determining the catalytic performance in the methanol electro-oxidation.

Mesoporous carbon materials were prepared using ordered silica templates. The Pt catalysts supported on mesoporous carbons were prepared by an impregnation method for use in the methanol electro-oxidation. The Pt/MC catalysts retained highly dispersed Pt particles on the supports. In the methanol electro-oxidation, the Pt/MC catalysts exhibited better catalytic performance than the Pt/Vulcan catalyst. The enhanced catalytic performance of Pt/MC catalysts resulted from large active metal surface areas. The catalytic performance was in the following order Pt/CMK-1 > Pt/CMK-3 > Pt/Vulcan. It was also revealed that CMK-1 with 3-dimensional pore structure was more favorable for metal dispersion than CMK-3 with 2-dimensional pore arrangement. It is eoncluded that the metal dispersion was a critical factor determining the catalytic performance in the methanol electro-oxidation. 

For a supported metal catalyst, the BET method yields the total surface area of support and metal. If we perform our measurements in the chemisorption domain, for example with H2 or CO at room temperature, adsorption is limited to the metallic phase, providing a way to determine the dispersion of the supported phase. 

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