Metal nanoparticles synthesis hydrogenation reactions

The wide range of desired functionalities on the surface of catalysts that includes, for example, strong acid sites for cracking reaction, mild acid-base pairs for the synthesis of fine chemicals, redox properties for oxidation reactions, or metal nanoparticles for hydrogenation or electrochemical applications seems to complicate the derivation of general rules with respect to catalyst synthesis. It is, however, accepted without controversy that good catalysts feature the following characteristics ... 

This approach of using 2D and 3D monodisperse nanoparticles in catalytic reaction studies ushers in a new era that will permit the identification of the molecular and structural features of selectivity [4,9]. Metal particle size, nanoparticle surface-structure, oxide-metal interface sites, selective site blocking, and hydrogen pressure have been implicated as important factors influencing reaction selectivity. We believe additional molecular ingredients of selectivity will be uncovered by coupling the synthesis of monodisperse nanoparticles with simultaneous studies of catalytic reaction selectivity as a function of the structural properties of these model nanoparticle catalyst systems. 

This method ensures the deposition of very reactive metal nanoparticles that require no activation steps before use. We shall review here the following examples of catalytic reactions that are of interest in line chemical synthesis (a) the hydrogenation of substituted arenes, (b) the selective hydrogenation of a, 3-unsaturated carbonyl compounds, (c) the arylation of alkenes with aryl halides (Heck reaction). The efficiency and selectivity of commercial catalysts and of differently prepared nanosized metal systems will be compared. 

The team of Crooks is involved in the synthesis and the use of dendrimers and, more particularly, poly(amidoamine) dendrimers (PAMAM), for the preparation of dendrimer-encapsulated mono- or bimetallic nanoparticles of various metals (Pt, Pd, Cu, Au, Ag, Ni, etc.) [55, 56]. The dendrimers were used as nanocatalysts for the hydrogenation of allyl alcohol and N-isopropylacrylamide or other alkenes under different reaction conditions (water, organic solvents, biphasic fluorous/or-ganic solvents or supercritical COz). The hydrogenation reaction rate is dependent on dendrimer generation, as higher-generation dendrimers are more sterically... 

Fig. 3. Schematic illustration of the synthesis of metal nanoparticles within dendrimer templates. The composites are prepared by mixing of the dendrimer and metal ion, and subsequent chemical reduction. These materials can be immobilized on electrode surfaces where they serve as electrocatalysts or dissolved in essentially any solvent (after appropriate end-group functionalization) as homogeneous catalysts for hydrogenation and other reactions...

The in situ reduction of the precursor [lr(COD)Cl]2 dispersed in BMI-PF at 75 °C and under 4atm of H2 provided a suitable medium for the synthesis of lr(0) nanoparticles, and represents an ideal system for the biphasic hydrogenation reactions of several olefins (Table 15.3) [24]. Of note, the TOP observed for this system (6000 h at 1200 rpm and 75 °C) was considerably higher than those obtained under biphasic conditions by classical transition-metal catalyst precursors in ILs under similar reaction conditions [46-48]. 

Zhao et al (70) developed a method for the synthesis of dendrimer-encapsulated metal nanoparticles based on sorbing metal ions into (modified) PAMAM dendrimers followed by a reduction. Dendrimers encapsulating copper, palladium, and platinum nanoparticles have been prepared. Hydroxyl-terminated PAMAM dendrimers were used to prepare encapsulated palladium (PAMAM generations 4, 6, and 8) and platinum (PAMAM generations 4 and 6) nanoparticles. The dendrimer-encapsulated palladium and platinum nanocomposites catalyzed the hydrogenation reaction of allyl alcohol and N-isopropyl acrylamide in water 71). 

Transition metal nanoparticles supported on different substrates are used as catalysts for different reactions, such as hydrogenations and enantioselective-synthesis of organic compounds, oxidations and epoxidations, reduction, and decomposition [24,25], Among the supports that have been applied in the preparation of supported transition metal nanoparticles are active carbon, silica, titanium dioxide, and alumina. 

Dendrimers and cyclodextrins constitute an interesting stabihzing mode in the synthesis of metal nanoparticles. They can bring selectivity in some catalytic reactions, such as olefin or arene hydrogenations, due to their specific structure. 

Several approaches have recently been developed that directly apply natural architectures for artificial chanical reactions, some of which are detailed in different chapters of this book. Although not classified as homogeneous catalysis, the reduction of metal salts inside nanoreactors could be the first step on the way to reactivity with the corresponding metal coUoids or nanoparticles in e.g. hydrogenation reactions. A variety of carrier systems have been studied lately, including virus capsids, polymeric micelles, miniemulsions and hollow core-shell particles, as nanoreactors and hosts for the synthesis and encapsnlation of well-defined, stable nanoparticles. ... 

The dendrimer-mediated synthesis of metal nanoparticles was initiated by the pioneering work of Tomalia [48] and Crooks [49] on synthesizing copper nanoclusters in 1998. In 1999, Crooks and Zhao reported two studies on the synthesis of Pt [50] and Pd [51] nanoparticles with PAMAM Starburst dendrimers. In these two studies, the synthesized Pt and Pd nanoparticles were used in electrocatalytic oxygen reduction and homogeneous hydrogenation reactions, respectively. 

Microemulsions have been used as confined reaction media during the past two decades, since, due to the very small size of the droplets, they can act as microreactors capable to control the size of the particles and at the same time to inhibit the aggregation by adsorption of the surfactants on the particle surface when the particle size approaches that of the microreactor droplet. The synthesis of nanoparticles using reactions in microemulsions was first described by Boutonnet and cowoikers They synthesized monodispersed metal particles of Pt, Pd, Rh and Ir by reduction of metal salts with hydrogen or hydrazine in water in oil (w/o) microemulsions. Since then, many different types of materials have been prepared using microemulsions, including metal carbonates, metal oxides, " metal chalcogenides, "" polymers," etc. 

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