Properties and Reactivities of Nanostructured Materials

An examination of recent information on the properties, structures, and reactivities of nanostructured materials indicates the importance of 

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Both the discovery of new synthesis processes for nanostructured materials and the demonstration of the highly reactive properties of these materials have increased rapidly within recent years. The new synthesis processes have made available nanostructured materials in a wide variety of compositions of metal oxides and metals supported on metal oxides, which have led to recognition of their exceptional chemical, physical, and electronic properties. The objective of this review is to provide recent results on synthesis of nanostructured materials using the novel processes that were developed in these laboratories recently and to contrast them to other important, new methods. Because some of the most important applications of nanostructured materials are as catalysts for chemical processing, several key reports on enhanced catalytic reactivity of nanostructured grains will be discussed along with the pertinent theory responsible for controlling both activity and selectivity of these new catalysts. 

The chapters in this volume present detailed insights into the synthesis-structure-properties relationships of nanostructured materials. In particular, the catalytic and photocatalytic properties of nanoclusters and nanostructured materials with ultrahigh surface-to-volume ratio are demonstrated. The gas absorption characteristics and surface reactivity of nanoporous and nanocrystalline materials are shown for various separation and reaction processes. In addition, the structural manipulation, quantum confinement effects, transport properties, and modeling of nanocrystals and nanowires are described. The biological functionality and bioactivity of nanostructured ceramic implants are also discussed. 

The study of small and intermediate-sized clusters has become an important research field because of the role clusters play in the explanation of the chemical and physical properties of matter on the way from molecules to solids/ Depending on their size, clusters can show reactivity and optical properties very different from those of molecules or solids. The great interest in silicon clusters stems mainly from the importance of silicon in microelectronics, but is also due in part to the photoluminescence properties of silicon clusters, which show some resemblance to the bright photoluminescence of porous silicon. Silicon clusters are mainly produced in silicon-containing plasma as used in chemical vapor deposition processes. In these processes, gas-phase nucleation can lead to amorphous silicon films of poor quality and should be avoided.On the other hand, controlled production of silicon clusters seems very suitable for the fabrication of nanostructured materials with a fine control on their structure, morphological, and functional properties. ... 

Abstract The goal of catalyst development is to be able to adjust the structure and composition of catalytic materials to obtain the optimal electronic properties for desired chemical reactivity. Key features of the electronic stmcture that influence the reactivity of nanostructured catalysts are reviewed. Conclusions derived from the DPT electronic structure and the surface reactivity computations, with emphasis on the catalyst property intrinsically governed by the local, site-specific interactions, for nanostructured catalysts are presented. 

The introduction of new synthetic techniques has led to the discoveries of many new electronic materials with improved properties [20-22]. However, similar progress has not been forthcoming in the area of heterogeneous catalysis, despite the accumulation of considerable information regarding structure-reactivity correlations for such catalysts [14-19]. The synthetic challenge in this area stems from the complex and metastable nature of the most desirable catalytic structures. Thus, in order to minimize phase separation and destruction of the most efficient catalytic centers, low-temperature methods and complicated synthetic procedures are often required [1-4]. Similar challenges are faced in many other aspects of materials research and, in general, more practical synthetic methods are required to achieve controlled, facile assembly of complex nanostructured materials [5-11]. 

Ill-defined carbon materials that provide a distinct nanostructure, such as spherical particles in the case of soot and carbon black, or hexagonally ordered cylindrical pores in the case of ordered mesoporous carbons, are not discussed here. Surface chemical, thus catalytic properties of these material are closer to carbon black or activated carbon [13], which is frequently reviewed [2-4]. Here, the higher degree of sp3 hybridization often results in a higher reactivity, however, at lower selectivity, as compared to nanocarbons exposing large basal plane fractions of the overall surface. 

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