Supported metals preparation methods, 36:61

It seems plausible that the catalytic activity of small metal particles would be influenced by the crystal structure. Yacaman et al. (118) have studied pentane hydrogenolysis over Rh -A C, Rh/Si02, Rh/C, Rh/Ti02, and Rh/MgO. The support and preparation method, all for particles of d < 5 nm, determined whether cubooctahedrons or icosahedrons were formed, but the catalytic properties depended more on d than on crystal type. 

Today the most efficient catalysts are complex mixed metal oxides that consist of Bi, Mo, Fe, Ni, and/or Co, K, and either P, B, W, or Sb. Many additional combinations of metals have been patented, along with specific catalyst preparation methods. Most catalysts used commercially today are extmded neat metal oxides as opposed to supported impregnated metal oxides. Propylene conversions are generally better than 93%. Acrolein selectivities of 80 to 90% are typical. 

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. 

PtRu nanoparticles can be prepared by w/o reverse micro-emulsions of water/Triton X-lOO/propanol-2/cyclo-hexane [105]. The bimetallic nanoparticles were characterized by XPS and other techniques. The XPS analysis revealed the presence of Pt and Ru metal as well as some oxide of ruthenium. Hills et al. [169] studied preparation of Pt/Ru bimetallic nanoparticles via a seeded reductive condensation of one metal precursor onto pre-supported nanoparticles of a second metal. XPS and other analytical data indicated that the preparation method provided fully alloyed bimetallic nanoparticles instead of core/shell structure. AgAu and AuCu bimetallic nanoparticles of various compositions with diameters ca. 3 nm, prepared in chloroform, exhibited characteristic XPS spectra of alloy structures [84]. 

The second general method, IMPR, for the preparation of polymer supported metal catalysts is much less popular. In spite of this, microencapsulation of palladium in a polyurea matrix, generated by interfacial polymerization of isocyanate oligomers in the presence of palladium acetate [128], proved to be very effective in the production of the EnCat catalysts (Scheme 3). In this case, the formation of the polymer matrix implies only hydrolysis-condensation processes, and is therefore much more compatible with the presence of a transition metal compound. That is why palladium(II) survives the microencapsulation reaction... 

Xin and co-workers modified the alkaline EG synthesis method by heating the metal hydroxides or oxides colloidal particles in EG or EG/water mixture in the presence of carbon supports, for preparing various metal and alloy nanoclusters supported on carbon [20-24]. It was found that the ratio of water to EG in the reaction media was a key factor influencing the average size and size distribution of metal nanoparticles supported on the carbon supports. As shown in Table 2, in the preparation of multiwalled carbon nanotube-supported Pt catalysts... 

Mao and Mao invented a method for synthesizing supported metal catalysts with small metal nanoparticles (1-3 nm) even at high metal loadings (30-50 wt.%) [25]. The obtained metal catalysts exhibited superior electrocatalytic performance in fuel cells. In this invention, the unprotected metal nanocluster colloids prepared according... 

The small metal particle size, large available surface area and homogeneous dispersion of the metal nanoclusters on the supports are key factors in improving the electrocatalytic activity and the anti-polarization ability of the Pt-based catalysts for fuel cells. The alkaline EG synthesis method proved to be of universal significance for preparing different electrocatalysts of supported metal and alloy nanoparticles with high metal loadings and excellent cell performances. 

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,... 

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)]. 

Chromium zeolites are recognised to possess, at least at the laboratory scale, notable catalytic properties like in ethylene polymerization, oxidation of hydrocarbons, cracking of cumene, disproportionation of n-heptane, and thermolysis of H20 [ 1 ]. Several factors may have an effect on the catalytic activity of the chromium catalysts, such as the oxidation state, the structure (amorphous or crystalline, mono/di-chromate or polychromates, oxides, etc.) and the interaction of the chromium species with the support which depends essentially on the catalysts preparation method. They are ruled principally by several parameters such as the metal loading, the support characteristics, and the nature of the post-treatment (calcination, reduction, etc.). The nature of metal precursor is a parameter which can affect the predominance of chromium species in zeolite. In the case of solid-state exchange, the exchange process initially takes place at the solid- solid interface between the precursor salt and zeolite grains, and the success of the exchange depends on the type of interactions developed [2]. The aim of this work is to study the effect of the chromium precursor on the physicochemical properties of chromium loaded ZSM-5 catalysts and their catalytic performance in ethylene ammoxidation to acetonitrile. 

An alternative approach for the preparation of supported metal catalysts is based on the use of a microwave-generated plasma [27]. Several new materials prepared by this method are unlikely to be obtained by other methods. It is accepted that use of a microwave plasma results in a unique mechanism, because of the generation of a nonthermodynamic equilibrium in discharges during catalytic reactions. This can lead to significant changes in the activity and selectivity of the catalyst. 

Recently, Chaudhari compared the activity of dispersed nanosized metal particles prepared by chemical or radiolytic reduction and stabilized by various polymers (PVP, PVA or poly(methylvinyl ether)) with the one of conventional supported metal catalysts in the partial hydrogenation of 2-butyne-l,4-diol. Several transition metals (e.g., Pd, Pt, Rh, Ru, Ni) were prepared according to conventional methods and subsequently investigated [89]. In general, the catalysts prepared by chemical reduction methods were more active than those prepared by radiolysis, and in all cases aqueous colloids showed a higher catalytic activity (up to 40-fold) in comparison with corresponding conventional catalysts. The best results were obtained with cubic Pd nanosized particles obtained by chemical reduction (Table 9.13). 

The regeneration of deactivated immobilized catalysts is not as easy as with conventional supported metal catalysts, where combustion of the deposited material is frequently used. Because such a procedure would destroy the organic ligands, one must resort to washing procedures. However, when this method fails, attempts must be made to recover the metal and the ligand, and to prepare a fresh catalyst. In principle, it is possible to recover the metal complexes from physically and ionically immobilized catalysts. This can also be done from covalently bound catalysts by using an easily hydrolyzable linker. 

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