Catalysis bimetallic systems

ViUa A, Wang D, Su DS, Prati L. New challenges in gold catalysis bimetallic systems. Catal Sci Technol. 2015 5 55-68. 

For a further discussion of the structure and properties of bimetallic systems, see Sections 2.6 and 3.2.3 for the preparation of bimetallic catalysts, see Section 4.6 and for the mechanisms by which they work in oxidations, see Section 8.2.2. Most textbooks of physical chemistry have sections on adsorption and catalysis, but they frequently focus on studies made under ultra-high vacuum conditions with single crystal surfaces. While this work produces beautiful pictures, it has limited relevance to the more mundane world of practical catalysis. Other introductory treatments of about the level of this chapter, or slightly more advanced, are available,5,7,11 as are deeper discussions of the kinetics of catalysed reactions.12 14 Industrial processes using catalysts have also been described in detail.15,16... 

Bimetallic nanoparticles constitute suitable model systems for studying alloying effects in catalysis. In particular, palladium-based bimetallic systems were developed in order to increase the selectivity... 

The selectivity aspect of catalysis with bimetallic systems is again illustrated... 

Alloy-like bimetallic particles play an important role in heterogeneous catalysis. Numerous papers have discussed the gold-palladium system. The mutual influence of different neighboring atoms leads to catalytic behavior which is often considerably different (and sometimes better) than that of monometallic species. Electronic effects in shell-like structured bimetallic systems have, however, rarely been investigated. 

Multicomponent metallic hydrogenation catalysts, based on intermetallic compounds (IMC) of rare-earth elements with nickel, copper, cobalt, and other bimetallic systems. Most studies were devoted to two structural systems LnMs and LnMs, where Ln = La, Sm, Gd, Ce, Pr, and Nd and M = Ni (see Klabunovskii, Konenko s group 183,251,252 Compaiison of LnNis catalysts with Ni catalysts supported on oxides of Ln, show higher activities of the IMC s and their hydrides in hydrogenation of propene (100°C, 1 bar), where LaNis proved to be the most active catalyst... 

Gross A. Reactivity of bimetallic systems smdied from first principles. Topics in Catalysis 2006 37(l) 29-39. 

In contrast to oxidation in water, it has been found that 1-alkenes are directly oxidized with molecular oxygen in anhydrous, aprotic solvents, when a catalyst system of PdCl2(MeCN)2 and CuCl is used together with HMPA. In the absence of HMPA, no reaction takes place(100]. In the oxidation of 1-decene, the Oj uptake correlates with the amount of 2-decanone formed, and up to 0.5 mol of O2 is consumed for the production of 1 mol of the ketone. This result shows that both O atoms of molecular oxygen are incorporated into the product, and a bimetallic Pd(II) hydroperoxide coupled with a Cu salt is involved in oxidation of this type, and that the well known redox catalysis of PdXi and CuX is not always operalive[10 ]. The oxidation under anhydrous conditions is unique in terms of the regioselective formation of aldehyde 59 from X-allyl-A -methylbenzamide (58), whereas the use of aqueous DME results in the predominant formation of the methyl ketone 60. Similar results are obtained with allylic acetates and allylic carbonates[102]. The complete reversal of the regioselectivity in PdCli-catalyzed oxidation of alkenes is remarkable. 

Since 1976 until present time Toshima-t5q)e nanocolloids always had a major impact on catalysis and electrocatalysis at nanoparticle surfaces [47,210-213,398-407]. The main advantages of these products lie in the efficient control of the inner structure and morphology especially of bimetallic and even multimetallic catalyst systems. 

On the one hand, this mechanistic study represents the culmination of many preceding studies. On the other hand, this, together with several other recent developments, represents a new generation of organozirconium chemistry characterized by (i) Zr catalysis, (ii) bimetallic and multimetallic systems, in which bi- and multimetallic interplay is significant, and (iii) significant roles of various 0-bond metatheses. 

Conventionally, organometallic chemistry and transition-metal catalysis are carried out under an inert gas atmosphere and the exclusion of moisture has been essential. In contrast, the catalytic actions of transition metals under ambient conditions of air and water have played a key role in various enzymatic reactions, which is in sharp contrast to most transition-metal-catalyzed reactions commonly used in the laboratory. Quasi-nature catalysis has now been developed using late transition metals in air and water, for instance copper-, palladium- and rhodium-catalyzed C-C bond formation, and ruthenium-catalyzed olefin isomerization, metathesis and C-H activation. Even a Grignard-type reaction could be realized in water using a bimetallic ruthenium-indium catalytic system [67]. 

The Pt-Au systemhasbeen a valuable system to test DENs potential forpreparing NP systems of interest to the heterogeneous catalysis community. It is synthetically challenging, characterized by a wide bulk miscibility gap (18 to 98% Pt), and bimetallic NPs within this gap are unavailable by traditional routes. Nuzzo and coworkers have shown that bulk phase diagrams may not necessarily hold true for NPs " and results with the Pt-Au system support this conclusion provided appropriate syntheses are available. Utilizing Cu displacement syntheses, these substantial... 

On the other hand, hi- or multi-metallic supported systems have been attracting considerable interest in research into heterogeneous catalysis as a possible way to modulate the catalytic properties of the individual monometalUc counterparts [12, 13]. These catalysts usually show new catalytic properties that are ascribed to geometric and/or electronic effects between the metalUc components. Of special interest is the preparation of supported bimetallic catalysts using metal carbonyls as precursors, since the milder conditions used, when compared with conventional methods, can render catalysts with homogeneous bimetallic entities of a size and composition not usually achieved when conventional salts are employed as precursors. The use of these catalysts as models can lead to elucidation of the relationships between the structure and catalytic behavior of bimetalUc catalysts. 

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