Properties of Nanoparticles

Analagously to metal oxides, the properties of metals change when the soUd is constituted by particles and the size of these particles enters the nanomehic regime. Relevant to this chapter is the catalytic activity of gold nanoparticles, a 

The importance of gold nanoparticles in catalysis derives in part from the wealth of information and reliable experimental procedures to form these nanoparticles in different sizes and, even different shapes [7]. There are basically two different procedures to form gold nanoparticles, depending on whether they are going to be dispersed in a liquid or supported on a soUd. 

To give an idea of the monodispersity that can be achieved. Fig. 12.3 shows a transmission electron microscopy image of a colloidal gold sample prepared from 

HAuCLj following the conventional two-phase NaBH4 reduction procedure. Concerning the experimental procedures for the preparation of gold nanoparticles, the situation is that there are reliable protocols to prepare gold nanopartides of a few nanometers and a given dispersit) [37, 38]. 

Obviously, as the number of gold atoms grows the size of the duster increases and the proportion of atoms on the external surface with respect to those located internally decrease. Table 12.1 lists the percentage of external atoms for those full-shell gold clusters previously mentioned. Notice that 1 and 2nm size dusters 

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The uncertainty principle is negligible for macroscopic objects. Electronic devices, however, are being manufactured on a smaller and smaller scale, and the properties of nanoparticles, particles with sizes that range from a few to several hundred nanometers, may be different from those of larger particles as a result of quantum mechanical phenomena, (a) Calculate the minimum uncertainty in the speed of an electron confined in a nanoparticle of diameter 200. nm and compare that uncertainty with the uncertainty in speed of an electron confined to a wire of length 1.00 mm. (b) Calculate the minimum uncertainty in the speed of a I.i+ ion confined in a nanoparticle that has a diameter of 200. nm and is composed of a lithium compound through which the lithium ions can move at elevated temperatures (ionic conductor), (c) Which could be measured more accurately in a nanoparticle, the speed of an electron or the speed of a Li+ ion ... 

In order to make practical use of the physical properties of nanoparticles, whether individual or collective, one has to find a way to address them. If we leave out the near field techniques, this in turn requires that the particles be monodisperse and organized in two or three dimensions. It is therefore necessary to imagine techniques allowing the self-organization and even, ideally, the crystallization of nanoparticles into super-lattices. 

The physical properties of metal nanoparticles are very size-dependent. This is clear for their magnetic properties, for which the shape anisotropy term is very important. This is also true for the optical properties of nanoparticles displaying plasmon bands in the visible range (Cu, Ag, Au) and for 111-V... 

The preparation and study of metal nanoparticles constitutes an important area of current research. Such materials display fascinating chemical and physical properties due to their size [62, 63]. In order to prevent aggregation, metal nanoparticles are often synthesized in the presence of ligands, functionalized polymers and surfactants. In this regard, much effort has focused on the properties of nanoparticles dispersed into LCs. In contrast, the number of nanoparticles reported that display liquid crystal behavior themselves is low. Most of them are based on alkanethiolate stabilized gold nanoparticles. 

The most important information about the nanoparticles is the size, shape, and their distributions which crucially influence physical and chemical properties of nanoparticles. TEM is a powerful tool for the characterization of nanoparticles. TEM specimen is easily prepared by placing a drop of the solution of nanoparticles onto a carbon-coated copper microgrid, followed by natural evaporation of the solvent. Even with low magnification TEM one can distinguish the difference in contrast derived from the atomic weight and the lattice direction. Furthermore, selective area electron diffraction can provide information on the crystal structure of nanoparticles. 

The environment (e.g. the substrate) of the nanoparticles is a critical experimental parameter, which should be inert with respect to the nanoparticles. In the case of gold the native Si02 covered Si(l 0 0) seems to be an environment without any influence on the valence band of Au nanoparticles. The chemical and catalytic properties which are probably strongly correlated with the electronic structures of different systems, give another possibility to use and check the size dependent properties of nanoparticles. 

Mossbauer spectroscopy has been extensively used for studies of nanostructured materials and several reviews on magnetic nanoparticles have been published, see e.g. [6-8, 46 8]. The magnetic properties of nanoparticles may differ from those of bulk materials for several reasons. The most dramatic effect of a small particle size is that the magnetization direction is not stable at finite temperatures, but fluctuates. 

Lanthanides with fractional valences have II, III and IV valences, as well as mixed II/III and III/IV valences. Depending on temperature and pressure, the degree of oxidation can change. This effect may result in a change in the different properties of nanoparticles, such as the stability, heat capacity, conductivity and magnetic susceptibility [218]. Valence fluctuation phenomena have been reported to occur... 

Nanotechnology is an evolving research area especially in materials and biotechnological sciences. First studies have shown that the special properties of nanoparticles can give rise to highly active and selective catalysts to enable chemists to perform entirely novel transformations. Discussion and evaluation of the potential of nanoparticles for chemical research in a pharmaceutical company with experts in the field was needed. Other areas in catalysis like biotransformations and metal catalyst screening and development continue to expand the possibilities for the manufacturing of test compounds and development candidates. 

Both nanospheres and nanocapsules are prepared from either a polymerization reaction of dispersed monomers or from a solvent dispersion procedure using preformed polymers. In many instances, the latter procedure using preformed polymer is desirable, as potential reactions between drug and monomer are avoided and the potential toxicity of residual monomers, surfactant, and initiator is reduced [37], The final properties of nanoparticles, such as their size, morphology, drug loading, release characteristics, and biodisti-bution, are all influenced by the method of preparation [38],... 

It is difficult to predict the effect of surface functionalization on the optical properties of nanoparticles in general. Surface ligands have only minor influence on the spectroscopic properties of nanoparticles, the properties of which are primarily dominated by the crystal field of the host lattice (e.g., rare-earth doped nanocrystals) or by plasmon resonance (e.g., gold nanoparticles). In the case of QDs, the fluorescence quantum yield and decay behavior respond to surface functionalization and bioconjugation, whereas the spectral position and shape of the absorption and emission are barely affected. 

Previous studies in conventional reactor setups at Philip Morris USA have demonstrated the significant effectiveness of nanoparticle iron oxide on the oxidation of carbon monoxide when compared to the conventional, micron-sized iron oxide, " as well as its effect on the combustion and pyrolysis of biomass and biomass model compounds.These effects are derived from a higher reactivity of nanoparticles that are attributed to a higher BET surface area as well as the coordination of unsaturated sites on the surfaces. The chemical and electronic properties of nanoparticle iron oxide could also contribute to its higher reactivity. In this work, we present the possibility of using nanoparticle iron oxide as a catalyst for the decomposition of phenolic compounds. 

It is not the subject of this chapter to cover all domains of the catalytic properties of nanoparticles modified by organometallics. In particular, we will not cover the work of Bormeman on metallic particles have been modified by organoaluminum compounds. 

Properties of nanoparticles (nuclei) are different from those of the bulk counterparts. Metastable phases may nucleate first because nanoparticles of these phases are more stable (e.g., due to low surface energy) than the nanoparticles of phases that are more stable in bulk (Ranade et al., 2002). 

Interest in research into new synthetic routes for semiconductor nanocrystallites has now increased as devices based upon such materials have been fabricated [3-5]. Theoretical models predicting the optical properties of semiconductors nanoparticles are available [6-10] but the properties of nanoparticles obtained by any new synthetic procedure are hard to anticipate. High purity, monodispersity and the ability to control the surface derivatiza-tion are the requirements for this system. 

There are two very broad, general conclusions resulting from the above review. The first is that MoS2-type nanoparticles are very different than other types of semiconductor nanoparticles. Nanoparticles of several different types of semiconductors, such as CdSe, CdS, and InP, have been extensively studied. Experimental and theoretical studies have elucidated much of their spectroscopy, photophysics, and dynamics. The results reviewed above are, in many places, in sharp contrast with those obtained on other types of quantum dots. This does not come as a surprise. The properties of the bulk semiconductor are reflected in those of the nanoparticle, and properties of layered semiconductors are vastly different from those of semiconductors having three-dimensional crystal structures. Although the electronic and spectroscopic properties of nanoparticles are strongly influenced by quantum confinement effects, the differences in the semiconductors cause there to be few generalizations about semiconductor quantum dots that can be made. 

An intense femtosecond laser spectroscopy-based research focusing on the fast relaxation processes of excited electrons in nanoparticles has started in the past decade. The electron dynamics and non-linear optical properties of nanoparticles in colloidal solutions [1], thin films [2] and glasses [3] have been studied in the femto- and picosecond time scales. Most work has been done with noble metal nanoparticles Au, Ag and Cu, providing information about the electron-electron and electron-phonon coupling [4] or coherent phenomenon [5], A large surface-to-volume ratio of the particle gives a possibility to investigate the surface/interface processes. 

The uncertainty principle is negligible for. macroscopic objects. Electronic devices, however, are being manufactured on a smaller and smaller scale so that the properties of nanoparticles, particles whose sizes range from a few to several hundred nanometers, may be different from those of larger particles due to quantum mechanical phenomena, (a) Calculate the minimum uncertainty in the speed of an electron confined in a nanoparticle with a diameter of... 

The concept of local perturbations of the director around nanoparticles, often linked to homeotropic anchoring to the nanoparticle surface, is a concept often brought forward in discussions of thermal, optical and electro-optic properties of nanoparticle-doped nematic liquid crystals, which adds a slightly different perspective to the invisibility of smaller particles in aligned nematics. This appears to be of particular relevance for particles coated with either hydrocarbon chains or pro-mesogenic as well as mesogenic units. 

Our group pursued another approach of combining the properties of nanoparticles with chiral nematic liquid crystal phases. The idea was to decorate gold nanoparticles with chiral molecules known to be strong inducers of chiral nematic phases. To realize the idea, we prepared a series of alkylthiol-capped gold nanoparticles, either pure monolayer or mixed monolayer, with all or about every second of the alkylthiols end-functionalized with (5)-naproxen (e.g., 6 in Fig. 11) [349]. 

H.C. Schwarzer, W. Peukert, Prediction of aggregation kinetics based on surface properties of nanoparticles, Chem. Eng. Sci., in press. 

The size-dependent properties of nanoparticles differ greatly from the corresponding bulk materials. An example is the size quantization phenomenon commonly observed in II-VI and III-V inorganic semiconductor nanocrystals.6 During the intermediate transition towards that of the bulk metal (usually between 2 and 20 nm), localization of electrons and holes in a confined volume causes an increase in its effective optical band gap as the size of the nanoparticle decreases, observed as a blue shift in its optical spectrum. Bms predicted that there should also be a dependence on the redox potential for these same classes of quantum dots.7 Bard and coworkers showed this experimentally and have reported on the direct observation between the... 

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