Preparation supported mixed metals

The aerogel-prepared metal oxide nanoparticles constitute a new class of porous inorganic materials because of their unique morphological features such as crystal shape, pore structure, high pore volume, and surface areas. Also, it is possible to load catalytic metals such as Fe or Cu at very high dispersions on these oxide supports and hence the nanocrystalline oxide materials can also function as unusual catalyst supports. Furthermore, these oxides can be tailored for desired Lewis base/Lewis acid strengths by incorporation of thin layers of other oxide materials or by preparation of mixed metal oxides. 

Supported mixed metal catalysts can be prepared by almost any of the procedures described above for the production of monometallic species. The discussion concerning the surface composition of these multimetallic species presented in Chapter 12 applies to supported catalysts as well but may be modified by the presence of very small crystallites in the supported catalysts. 2> 3 The factors presented above concerning the location of the metal in the support particle are also applicable here as well and can be used to prepare bimetallic catalysts having specific distribution profiles. 

This organometallic approach to the preparation of mixed metals has also been used to prepare mixed metal species containing tin.201-206 As shown in Fig. 13.21 the reaction of tetraalkyl tin with silica or alumina supported platinum. 

Supported mixed metal catalysts are also prepared by other means such as the deposition of bimetallic colloids onto a support O and the decomposition of supported bimetallic cluster compounds.208 The photocatalytic codeposition of metals onto titania was also attempted with mixed results.209 with a mixture of chloroplatinic acid and rhodium chloride, very little rhodium was deposited on the titania. With aqueous solutions of silver nitrate and rhodium chloride, more rhodium was deposited but deposition was not complete. In aqueous ammonia, though, deposition of both silver and rhodium was complete but the titania surface was covered with small rhodium crystallites and larger silver particles containing some rhodium. With a mixture of chloroplatinic acid and palladium nitrate both metals were deposited but, while most of the resulting crystallites were bimetallic, the composition varied from particle to particle.209... 

Reactions of organometallic complexes with supported metal particles should be used to extend the range of preparation of mixed metal particles. 

An alternative method of preparation of bimetallic catalysts [11-14] is based on the direct interaction of metal carbonyl clusters with surfaces of supported metals under mild conditions. In this work, a comparison is made of various methods of preparation of mixed metallic particles by interaction of organometallic compounds with metal surfaces. 

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. 

These routes rely on the direct transformation of soluble molecular species into supported metal (or mixed metal) particles. One method that has recently become popular is the "polyol" method. This takes a solution of metal salts, the carbon support, and a polyalcohol such as ethylene glycol. On heating, the polyol acts as both stabilizer and reductant, forming reduced metal particles on the carbon. It has been used successfully to prepare Ft and PtRu catalysts. ... 

For mixed metal oxides obtained from their hydroxide or carbonate precursors after calcination, it is generally difficult to determine whether the as-prepared precursor is a single-phase or multiphase solid solution [35]. Non-aqueous solvents appear superior for achieving two dissimilar metal oxides such as MM Oz or MM 04 precipitates such reactions cannot be carried out simultaneously in aqueous solution due to the large variations in pH necessary to induce precipitations [41,42]. Table 6.1 summarizes some of the nanoparticulate semiconducting metal oxides and mixed metal oxides prepared via co-precipitation techniques. The general procedure of achieving metal loaded nanoparticles on an oxide support is shown in Fig.6.5. 

Although with the selective removal proecdurc the active component and the support are usually verv intimately mixed, it is difficult to control the porous structure and/or the mechanical strength ol the result ing eatalyst bodies Nonetheless the procedure is difficult to beat for the production ol highly loaded supports The most well known example of selective removal, the preparation of Raney metals, where alu minum is selectively removed, leaves behind almost exclusively the desired active metal... 

Reaction-induced dispersion may be used as a substitute for conventional preparation methods for supported metal oxides (Wachs and Cai, 2001) it constitutes a particular case of solid—solid wetting, which is proposed to play an important role in catalyst preparation (Leyrer et al., 1990). Industrially relevant mixed metal oxide catalysts can be prepared by reaction-induced dispersion at temperatures that are significantly... 

Although hydrotalcites are relahvely stable (up to circa 500 °C), they are also of potential applicahon as precursors of mixed metal oxide catalysts, for example Reference [66]. Dehydrahon-rehydration equilibria account for the switching between hydrotalcites and mixed/supported metal oxides, which is somehmes termed the memory effect [67-69]. Recent advances have seen attempts to prepare highly dispersed LDH systems, such as those dispersed within mesoporous carbon [70]. Owing to widespread interest in their application, hydrotalcite catalysts have been the subject of a number of reviews, for example References [71-75]. Other layered-based systems have also attracted attention for application in catalysis, for example Reference [76]. 

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