Metallic nanoparticles chemical synthesis

The most intensive development of the nanoparticle area concerns the synthesis of metal particles for applications in physics or in micro/nano-electronics generally. Besides the use of physical techniques such as atom evaporation, synthetic techniques based on salt reduction or compound precipitation (oxides, sulfides, selenides, etc.) have been developed, and associated, in general, to a kinetic control of the reaction using high temperatures, slow addition of reactants, or use of micelles as nanoreactors [15-20]. Organometallic compounds have also previously been used as material precursors in high temperature decomposition processes, for example in chemical vapor deposition [21]. Metal carbonyls have been widely used as precursors of metals either in the gas phase (OMCVD for the deposition of films or nanoparticles) or in solution for the synthesis after thermal treatment [22], UV irradiation or sonolysis [23,24] of fine powders or metal nanoparticles. 

The intention of this chapter is to provide a general survey on the preparative methodologies for the size- and shape-selective synthesis of metallic nanoparticles that have emerged from the benches of chemical basic research during the last few decades and become established as practical standard protocols. Industrial scale-up, however, has only just started to test the economic viability of these procedures and to determine whether they can meet the challenges of a number of very specific applications. The commercial manufacture of such thermodynamically extremely unstable nanoparticles in defined sizes and shapes on the kilo-scale is still confronted by a number of major problems and it remains to be seen how these can be solved. 

The synthesis of bimetallic nanoparticles is mainly divided into two methods, i.e., chemical and physical method, or bottom-up and top-down method. The chemical method involves (1) simultaneous or co-reduction, (2) successive or two-stepped reduction of two kinds of metal ions, and (3) self-organization of bimetallic nanoparticle by physically mixing two kinds of already-prepared monometallic nanoparticles with or without after-treatments. Bimetallic nanoparticle alloys are prepared usually by the simultaneous reduction while bimetallic nanoparticles with core/shell structures are prepared usually by the successive reduction. In the preparation of bimetallic nanoparticles, one of the most interesting aspects is a core/shell structure. The surface element plays an important role in the functions of metal nanoparticles like catal5dic and optical properties, but these properties can be tuned by addition of the second element which may be located on the surface or in the center of the particles adjacent to the surface element. So, we would like to use following marks to inscribe the bimetallic nanoparticles composed of metal 1, Mi and metal 2, M2. 

Since nanoscale metal nanoparticles are applicable to a number of areas of technological importance, the nano-structured materials chemistry will occupy much attention of scientists. It is certain that controlling the primary structures of metal nanoparticles, that is, size, shape, crystal structure, composition, and phase-segregation manner is still most important, because these structures dominate the physical and chemical properties of metal nanoparticles. Now the liquid phase synthesis facilitates the precise control of the primary structures. 

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. 

In this chapter the potential of nanostructured metal systems in catalysis and the production of fine chemicals has been underlined. The crucial role of particle size in determining the activity and selectivity of the catalytic systems has been pointed out several examples of important reactions have been presented and the reaction conditions also described. Metal Vapor Synthesis has proved to be a powerful tool for the generation of catalytically active microclusters SMA and nanoparticles. SMA are unique homogeneous catalytic precursors and they can be very convenient starting materials for the gentle deposition of catalytically active metal nanoparticles of controlled size. 

M. (2008) One-minute synthesis of crystalline binary and ternary metal oxide nanoparticles. Chemical Communications, (7), 886-888. 

Jyothish, K., John, G., Vemula, P.K., Jadhav, S.R. and Francesconi, L.C. (2009) Self standing, metal nanoparticle embedded transparent films from multiarmed cardanol conjugates through in situ synthesis. Chemical Communications, 5368-5370. 

The approaches used for preparation of inorganic nanomaterials can be divided into two broad categories solution-phase colloidal synthesis and gas-phase synthesis. Metal and semiconductor nanoparticles are usually synthesized via solution-phase colloidal techniques,4,913 whereas high-temperature gas-phase processes like chemical vapor deposition (CVD), pulsed laser deposition (PLD), and vapor transfer are widely used for synthesis of high-quality semiconductor nanowires and carbon nanotubes.6,7 Such division reflects only the current research bias, as promising routes to metallic nanoparticles are also available based on vapor condensation14 and colloidal syntheses of high-quality semiconductor nanowires.15... 

Dendrimer interior functional groups and cavities can retain guest molecules selectively, depending on the nature of the guest and the dendritic endoreceptors, the cavity size, the structure, and the chemical composition of the peripheric groups. Two main methods are known for the synthesis of metal nanoparticles inside dendrimers. The first method consists of the direct reduction of dendrimer-encapsulated metal ions (Scheme 9.4) the second method corresponds to the displacement of less-noble metal clusters with more noble elements [54]. 

We showed that the application of PEG/CO2 biphasic catalysis is also possible in aerobic oxidations of alcohols [15]. With regard to environmental aspects it is important to develop sustainable catalytic technologies for oxidations with molecular oxygen in fine chemicals synthesis, as conventional reactions often generate large amoimts of heavy metal and solvent waste. In the biphasic system, palladium nanoparticles can be used as catalysts for oxidation reactions because the PEG phase both stabilises the catalyst particles and enables product extraction with SCCO2. 

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...

Electrochemical Synthesis of Bimetallic Particles. Most chemical methods for the preparation of metal nanoparticles are based at first on the reduction of the corresponding metal ions with chemical reagents to form metal atoms and then on the controlled aggregation of the obtained metal atoms. Instead of chemical reduction, an electrochemical process can be used to create metal atoms from bulk metal. Reetz and Hclbig proposed an electrochemical method including both oxidation of bulk... 

Usually there is a lot of effort required to make nanomaterials by electrochemical means. In aqueous solutions the electrodeposition of nanocrystalline metals requires pulsed electrodeposition and the addition of additives whose reaction mechanism hitherto has only been partly understood (see Chapter 8). A further shortcoming is that usually a compact bulk material is obtained instead of isolated particles. The chemical synthesis of metal or metal oxide nanoparticles in aqueous or organic solutions by colloidal chemistry, for example, also requires additives and often the desired product is only obtained under quite limited chemical conditions. Changing one parameter can lead to a different product. 

Solution phase chemical synthesis is a convenient way for making surfactant coated magnetic nanoparticles, as described in various reviews [12-18]. Monodisperse Co nanoparticles with standard deviation less than 10% are synthesized by decomposition of Co2(CO)8 [19-22] or Co(rj3-C8Hi3X n4-C8Hi2) [23] and reduction of cobalt salt [24,25] in the presence of oleic acid and trialkylphosphine, or trialkylphosphine oxide, or alkylamine. Monodisperse iron nanoparticles are normally prepared from decomposition of Fe(CO)5 [26-28]. However, metallic iron-based particles from this decomposition procedure are difficult to characterize due to the chemical instability. A recent synthesis using decomposition of Fe[NSiMe3)2]2 offers a promising approach to monodisperse Fe nanocrystals [29]. 

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