Catalysis using metallic nanoparticle composites

Here, we review the use of microgel particles as reactors for the immobilization of catalytically active metal nanoparticles or enzymes. The composite particles of microgels and the metal nanoparticles can be used for catalysis in aqueous media, that is, under very mild conditions [24-28], Thus, the composite systems allow us to do green chemistry [29] and conduct chemical reactions in a very efficient way. 

Besides clay-based nanocomposites, there has been huge discussion on the metallic and semiconductor-based hybrid materials. The ability of polymer materials to assemble into nanostructures describes the use of polymers providing exquisite order to nanoparticles. Finally, a discussion on potential applications of polymer—nanoparticle composites with a special focus on the use of dendrite polymers and nanoparticles for catalysis should follow (Polymer-Nanoparticle Composites Part 1 (Nanotechnology), 2010) (Figure 1.15). 

The composite particles of metal nanoparticles and spherical polyelectrolytes present robust systems that can be employed in catalysis More importantly, such metal nanoparticles can be used as effective catalysts in a green fashion, " that is, low temperature, easy removal of the catalyst, and low leaching of heavy metal into the product. 

Here we have reviewed our recent studies on metallic nanoparticles encapsulated in spherical polyelectrolyte brushes and thermosensitive core-shell microgels, respectively. Both polymeric particles present excellent carrier systems for applications in catalysis. The composite systems of metallic nanoparticles and polymeric carrier particles allow us to do green chemistry and conduct chemical reactions in a very efficient way. Moreover, in the case of using microgels as the carrier system, the reactivity of composite particles can be adjusted by the volume transition within the thermosensitive networks. Hence, the present chapter gives clear indications on how carrier systems for metallic nanoparticles should be designed to adjust their catalytic activity. 

Pure metal nanoparticles have shown exceptional catalytic properties which have motivated modem researchers to come up with innovative ideas to synthesize nanoparticles in a cost effective manner. Apart from catalysis, potential applications of metal nanoparticles ate well known in other fields such as pigments, electronic and magnetic materials, dmg deUvery etc. Here we report solution combustion synthesis method to synthesize transition metals (Ni, Cu and Co) in a single step process. Metal nitrates and glycine are used as synthesis precursors and dissolved in water to make a homogeneous aqueous solution which is combusted to produce metal nanoparticles with desired composition. 

There are different ways in which the nanoparticles prepared by ME-technique can be used in catalysis. The use of ME per se [16,17] implies the addition of extra components to the catalytic reaction mixture (hydrocarbon, water, surfactant, excess of a metal reducing agent). This leads to a considerable increase of the reaction volume, and a catal5fiic reaction may be affected by the presence of ME via the medium and solubilization effects. The complex composition of ME does not allow performing solvent-free reactions. 

Specific, surface confined reactions not only directly involve catalysis but also the built-up of sdf-assembled multilayers (see Fig. 9.1 (3)) with co-functionalities for more complex (bio-) catalytic systems such as proteins or the directed deposition of active metals. Furthermore, SAM on flat substrates can be used for the study and development of e.g. catalytic systems, but are not useful for large scale applications because they have very limited specific surface. Here, nanoparticle systems covered with 3D-SAMs are the ideal solution of combining the advantages of high surface area, defined surface composition and accessibility of proximal active catalytic centers. 

In recent years simultaneous progress in the understanding and engineering of block copolymer microstructures and the development of new templating strategies that make use of sol-gel and controlled crystalHzation processes have led to a quick advancement in the controlled preparation of nanoparticles and mesoporous structures. It has become possible to prepare nanoparticles of various shapes (sphere, fiber, sheet) and composition (metal, semiconductor, ceramic) with narrow size distribution. In addition mesoporous materials with different pore shapes (sphere, cyHndrical, slit) and narrow pore size distributions can be obtained. Future developments will focus on applications of these structures in the fields of catalysis and separation techniques. For this purpose either the cast materials themselves are already functional (e.g., Ti02) or the materials are further functionalized by surface modification. 

The two versions of the Miilheim electrochemical process provide colloidal solutions (e.g., in THF) of a variety of transition metal or bimetallic nanoparticles, and constitute a simple, clean and reliable alternative to chemical processes such as reduction by borohydrides in which the excess reducing agent and/or the oxidized form thereof have to be removed from the product (in fact, boron originating from boron hydrides is sometimes incorporated in the nanopaiticles) [26], But are these methods of any use in catalysis. One possibiUty is immobUization on soUd carriers, deUvering materials having islands of metal clusters of a predefined size. Moreover, they allow for the design of heterogeneous catalysts with well-defined compositional and structural features on a macroscopic and microscopic level. 

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