Electronic Properties of Nanoparticles

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 evident that the properties of nanoparticle structures depend not only on the individual particle size, particle shape, or the degree of size dispersion but also on their spatial distribution and the degree of aggregation or film formation. Therefore, before investigating the optical and electronic properties of nanoparticles, it is important to gain knowledge of how to control the particle size, particle density, and spatial distribution. 

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 ... 

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. 

Size reduction of metal particles results in several changes of the physico-chemical properties. The primary change is observed in the electronic properties of the metal particles which can be characterized by ultraviolet and X-ray photoelectron spectroscopy (UPS and XPS, respectively) as well as Auger-electron spectroscopy (AES) measurements. Furthermore, morphology of the metal nanoparticles is highly sensitive to the environment, such as ion-metal interaction (e.g. metal-support interaction)... 

In Section 2 the general features of the electronic structure of supported metal nanoparticles are reviewed from both experimental and theoretical point of view. Section 3 gives an introduction to sample preparation. In Section 4 the size-dependent electronic properties of silver nanoparticles are presented as an illustrative example, while in Section 5 correlation is sought between the electronic structure and the catalytic properties of gold nanoparticles, with special emphasis on substrate-related issues. 

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. 

Particle size and the method of nanoparticle preparation (including the capping agent used) determine the physical and electronic properties of the quantum dots produced. This gives chemists the unique ability to change the electronic and chemical properties of a semiconductor material by simply controlling particle size and preparative conditions employed. There are various methods for the preparation of nanoparticles however, not all methods work well for the preparation of compound semiconductor nanocrystallites. 

Supported nanoparticles (1-1.5 nm) based on Ru4Pt2 entities have been obtained by using a Ru4Pt2(CO)i8 precursor on carbon black and fullerene soot [63]. XANES analysis showed differences between the interaction of nanoparticles with both carbon black and fullerene supports. In particular, a change in the electronic properties of the nanoparticles on fullerene is proposed this change was related to a strong interaction between the nanoparticle and a surface-atom, probably via the formation of a Ru-carbide phase. 

The SMSI effect in Mn-promoted Ru/Ti02 catalysts was studied in more detail making use of the SSIMS technique, as well as with TEM, and selective chemisorption experiments. The SSIMS technique revealed the presence of TiO c forming two new surface sites, TiO -Ru and TiO-Mn. These species were found to be located at the immediate vicinity of the Ru nanoparticles. These new surface sites were considered to alter the electronic properties of the Ru metal surface and, as a consequence, the product selectivity. 

The addition of promoter elements to cobalt-based Fischer-Tropsch catalysts can affect (1) directly the formation and stability of the active cobalt phase structural promotion) by altering the cobalt-support interfacial chemistry, (2) directly affect the elementary steps involved in the turnover of the cobalt active site by altering the electronic properties of the cobalt nanoparticles electronic promotion) and (3) indirectly the behaviour of the active cobalt phase, by changing the local reaction environment of the active site as a result of chemical reactions performed by the promoter element itself synergistic promotion). 

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 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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