Metal nanoparticles surface functionalization

Metal nanoparticle surface modeling for relativistic density-functional calculations... 

It should be noted that, so far, these studies have been mostly confined to relatively simple organometallic molecular complexes, and none have involved nanoparticle molecules. Therefore, a fundamental question arises, when redox-active moieties are bound onto a transition-metal nanoparticle surface through conjugated chemical bonds will effective electronic communication take place between these particle-bound functional moieties This issue has been addressed in a recent study in which carbene-functionalized ruthenium nanoparticles are used as the nanoscale structural scaffold, and ferrocene moieties are exploited as the molecular probe because of well-known electrochemical and spectroscopic characteristics. 

Thiols and gold surfaces are ideal partners to write any kind of structure in nanometre dimensions. Artificial patterns of appropriately functionalized molecules can be used to bind metal nanoparticles specifically. Figure 25 gives an impression of the individual steps leading to a distinct cluster arrangement. 

Figure 25. Formation of an artificial structure of metal nanoparticles by dip pen nanolithography using an AFM (a), tip to transport functionalized thiol molecules onto a gold surface (b) and to trap the nanoparticles (c).

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. 

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. 

The rapid development of nanotechnology has revolutionized scientific developments in recent decades [1]. The synthesis, characterization, and application of functionalized nanoparticles are currently a very active field of research [2], Due to the size limitation of metal nanoparticles, they show very unique properties, which are called nano-size effect or quantum-size effect , which is different from those of both bulk metals and metal atoms. Such specific properties are usually dominated by the atoms located on the surface. In nanoparticles systems, the number of atoms located on the surface of the particles increases tremendously with decreasing of the particle diameter [3]. 

For transition and precious metals, thiols have been successfully employed as the stabilizing reagent (capping reagent) of metal nanoparticles [6]. In such cases, various functionalities can be added to the particles and the obtained nanoparticles may be very unique. It is well known that thiols provide good self-assembled monolayers (SAM) on various metal surfaces. When this SAM technique is applied to the nanoparticle preparation, nanoparticles can be covered constantly by functionalized moieties, which are connected to the terminal of thiol compounds. 

In 1994, thiols were firstly used as stabilizers of gold nanoparticles [6a]. Thiols form monolayer on gold surface [18] and highly stable nanoparticles could be obtained. Purification of nanoparticles can be carried out, which makes chemical method of metal nanoparticles a real process for nanomaterial preparation. Various thiol derivatives have been used to functionalize metal nanoparticles [6b, 19]. Cationic and anionic thiol compounds were used to obtain hydrosols of metal nanoparticles. Quaternary ammonium-thiol compounds make the nanoparticle surface highly positively charged [20]. In such cases, cationic nanoparticles were densely adsorbed onto oppositely charged surfaces. DNA or other biomolecule-attached gold nanoparticles have been proposed for biosensors [21]. 

Wet preparation of metal nanoparticles and their covalent immobilization onto silicon surface has been surveyed in this manuscript. Thiol-metal interaction can be widely used in order to functionalize the surface of metal nanoparticles by SAM formation. Various thiol molecules have been used for this purpose. The obtained functionalized particles can be purified to avoid the effect of unbounded molecules. On the other hand, hydrogen-terminated silicon surface is a good substrate to be covered by Si-C covalently bonded monolayer and can be functionalized readily by this link formation. Nanomaterials, such as biomolecules or nanoparticles, can be immobilized onto silicon surface by applying this monolayer formation system. 

Li et al. reported first on the decoration of hydrothermal carbon spheres obtained from glucose with noble metal nanoparticles [19]. They used the reactivity of as-prepared carbon microspheres to load silver and palladium nanoparticles onto then-surfaces, both via surface binding and room-temperature surface reduction. Furthermore, it was also demonstrated that these carbon spheres can encapsulate nanoparticles in their cores with retention of the surface functional groups. Nanoparticles of gold and silver could be encapsulated deep in the carbon by in situ hydrothermal reduction of noble-metal ions with glucose (the Tollens reaction), or by using silver nanoparticles as nuclei for subsequent formation of carbon spheres. Some TEM images of such hybrid materials are shown in Fig. 7.4. 

Pristine CNTs are chemically inert and metal nanoparticles cannot be attached [111]. Hence, research is focused on the functionalization of CNTs in order to incorporate oxygen groups on their surface that will increase their hydrophilicity and improve the catalyst support interaction (see Chapter 3) [111]. These experimental methods include impregnation [113,114], ultrasound [115], acid treatment (such as H2S04) [116— 119], polyol processing [120,121], ion-exchange [122,123] and electrochemical deposition [120,124,125]. Acid-functionalized CNTs provide better dispersion and distribution of the catalysts nanoparticles [117-120],... 

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...

DeVries et al.224 demonstrated experimentally that polar singularities form when a curved surface is coated with ordered monolayers (hairy-ball-theorem). The thiolates bound at the polar positions exchange faster than those in the bulk monolayer, thus allowing introduction of two—and only two—functional groups at the poles of a nanoparticle.224 This was the first example of divalent metal nanoparticles. This discovery opens up the path to new applications in the field of materials chemistry, and supramolecular chemistry, as stressed by Perepichka and Rosei.225 Undoubtedly, the regiochemical stability of these disubstituted nanoparticles and the chemical yield of their functionalization should be the subject of future studies. 

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