Supports silica supported metals

Fig. XVin-24. TVimover frequencies for methanation using silica-supported metals. (From Ref. 270.)...

Transition metals absorbed onto a solid support metal Pd,Pt, Ni, Rh support Carbon, alumina, silica solvent EtOH, EtOAc, Et20, hexanes, etc. 

In this article, we will discuss the use of physical adsorption to determine the total surface areas of finely divided powders or solids, e.g., clay, carbon black, silica, inorganic pigments, polymers, alumina, and so forth. The use of chemisorption is confined to the measurements of metal surface areas of finely divided metals, such as powders, evaporated metal films, and those found in supported metal catalysts. 

Raman spectroscopy has provided information on catalytically active transition metal oxide species (e. g. V, Nb, Cr, Mo, W, and Re) present on the surface of different oxide supports (e.g. alumina, titania, zirconia, niobia, and silica). The structures of the surface metal oxide species were reflected in the terminal M=0 and bridging M-O-M vibrations. The location of the surface metal oxide species on the oxide supports was determined by monitoring the specific surface hydroxyls of the support that were being titrated. The surface coverage of the metal oxide species on the oxide supports could be quantitatively obtained, because at monolayer coverage all the reactive surface hydroxyls were titrated and additional metal oxide resulted in the formation of crystalline metal oxide particles. The nature of surface Lewis and Bronsted acid sites in supported metal oxide catalysts has been determined by adsorbing probe mole-... 

The performance of a supported metal or metal sulfide catalyst depends on the details of its preparation and pretreatraent. For petroleum refining applications, these catalysts are activated by reduction and/or sulfidation of an oxide precursor. The amount of the catalytic component converted to the active ase cind the dispersion of the active component are important factors in determining the catalytic performance of these materials. This investigation examines the process of reduction and sulfidation on unsupported 00 04 and silica-supported CO3O4 catalysts with different C03O4 dispersions. The C03O4 particle sizes were determined with electron microscopy. X-ray diffraction (XRD), emd... 

In ecent years the utility of extended X-ray absorption fine structure UXAFS) as a probe for the study of catalysts has been clearly demonstrated (1-17). Measurements of EXAFS are particularly valuable for very highly dispersed catalysts. Supported metal systems, in which small metal clusters or crystallites are commonly dispersed on a refractory oxide such as alumina or silica, are good examples of such catalysts. The ratio of surface atoms to total atoms in the metal clusters is generally high and may even approach unity in some cases. 

Determination of Metal Precursor Mobilities During Pretreatment. Relative precursor mobilities were obtained by premixing the sllica-or alumina-supported metal catalysts with pure silica (Cab-O-Sll, grade M-5, Cabot Corp.) or pure alumina (Alon C, Cabot Corp.) In a 1 2 ratio prior to pretreatment. The catalyst and silica were ground together using a mortar and pestle for at least 0.5 hr. before they were placed in the Pyrex microreactor for pretreatment. 

The mechanical incorporation of active nanoparticles into the silica pore structure is very promising for the general synthesis of supported catalysts, although particles larger than the support s pore diameter cannot be incorporated into the mesopore structure. To overcome this limitation, pre-defined Pt particles were mixed with silica precursors, and the mesoporous silica structures were grown by a hydrothermal method. This process is referred to as nanoparticle encapsulation (NE) (Scheme 2) [16] because the resulting silica encapsulates metal nanoparticles inside the pore structure. 

Silica-supported metal (e.g., Pd/Si02) catalysts also have surface silanol groups that can react with the alkoxysilane groups of the complexes. These combination catalysts consist of a tethered complex on a supported metal. A Rh complex was tethered to the surface of a Pd/Si02 catalyst, and the tethered catalyst was more active for the hydrogenation of aromatic compounds than the free complex or the supported catalyst separately.33 It is possible that the H2 is activated on the supported metal and the hydrogen atoms migrate to the silica, where they react with the reactant molecules coordinated by the tethered complex. 

Kinetic Parameters for Ethane Hydrogenolysis on Silica-Supported Metals (16)... 

Specific catalytic activities of a number of silica-supported metals have been determined for the hydrogenolysis of ethane to methane (16, 29-31,... 

This method is certainly the oldest one described in the literature the first example concerns the ion exchange of [Pt(NH3)4]2+ and the surface of a sulfonated silica.15 Even now, the preparation of many heterogeneous catalysts (i.e., supported metal or oxide particles) involves as the first step the reaction of a coordination complex with the surface of an ionic solid such as alumina,... 

Davda, R. R. Shabaker, J. W. Huber, G. W. Cortright, R. D. Dumesic, J. A., Aqueous-phase reforming of ethylene glycol on silica-supported metal catalysts. Applied Catalysis B 2003,43,13-26. 

Both heterogeneous and homogeneous CO reduction catalyst recipes often contain electrophilic components such as silica supports, metal oxides, and A1Cl3 [1,5,33,34,35,36]. 

In hydrocarbon reforming processes the vapour of an alkane is passed over a supported metal catalyst such as platinum on silica or alumina. Dehydrocyclization, isomerization and cracking reactions all take place to... 

Grenoble and coworkers229 reported an important influence of the support on the water-gas shift activity of various metal catalysts. For example, the rate increased an order of magnitude when Pt was supported on alumina versus silica. Turnover numbers for alumina-supported metal catalysts decreased in the order Cu, Re, Co, Ru, Ni, Pt, Os, Au, Fe, Pd, Rh, and Ir, whereby the activity varied by 3 orders of magnitude, suggesting a correlation between activity of the metal and the heat of adsorption. To describe these differences in activity, the authors used a bifunctional model, involving chemisorption of water on alumina and CO on the metal, followed by association of the CO with the water to form a formic acid-like formate species, with subsequent decomposition via dehydrogenation on the metal sites (Scheme 55). 

Supported metal catalysts are used in a large number of commercially important processes for chemical and pharmaceutical production, pollution control and abatement, and energy production. In order to maximize catalytic activity it is necessary in most cases to synthesize small metal crystallites, typically less than about 1 to 10 nm, anchored to a thermally stable, high-surface-area support such as alumina, silica, or carbon. The efficiency of metal utilization is commonly defined as dispersion, which is the fraction of metal atoms at the surface of a metal particle (and thus available to interact with adsorbing reaction intermediates), divided by the total number of metal atoms. Metal dispersion and crystallite size are inversely proportional nanoparticles about 1 nm in diameter or smaller have dispersions of 100%, that is, every metal atom on the support is available for catalytic reaction, whereas particles of diameter 10 nm have dispersions of about 10%, with 90% of the metal unavailable for the reaction. 

The high-density polyethylene is linear and can be manufactured by (i) coordination polymerisation of monomer by triethyl aluminium and tritanium chloride, (ii) polymerisation with supported Metal Oxide Catalysts. Such as chromium or molybdenum oxides supported over alumina-silica bases. 

O2 adsorption, 28 38 surface modility, 28 34 surface structure, 28 30, 31 oxidation of CO on, 28 65 oxide-supported metal catalysts, 41 10, 11 -phosphine catalysts achiral, 25 83-85 recovery, 32 354-356, 367-369 selectivity, 30 348 platinum, 30 355 -silica catalysts... 

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).

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