Heterostructured materials

Here we report the synthesis and catalytic application of a new porous clay heterostructure material derived from synthetic saponite as the layered host. Saponite is a tetrahedrally charged smectite clay wherein the aluminum substitutes for silicon in the tetrahedral sheet of the 2 1 layer lattice structure. In alumina - pillared form saponite is an effective solid acid catalyst [8-10], but its catalytic utility is limited in part by a pore structure in the micropore domain. The PCH form of saponite should be much more accessible for large molecule catalysis. Accordingly, Friedel-Crafts alkylation of bulky 2, 4-di-tert-butylphenol (DBP) (molecular size (A) 9.5x6.1x4.4) with cinnamyl alcohol to produce 6,8-di-tert-butyl-2, 3-dihydro[4H] benzopyran (molecular size (A) 13.5x7.9x 4.9) was used as a probe reaction for SAP-PCH. This large substrate reaction also was selected in part because only mesoporous molecular sieves are known to provide the accessible acid sites for catalysis [11]. Conventional zeolites and pillared clays are poor catalysts for this reaction because the reagents cannot readily access the small micropores. 

SYNTHESIS AND CATALYSIS OF MESOPOROUS SILICA-HETEROSTRUCTURED MATERIALS BASED ON MONTMORILLONITE... 

Based on ion-exchange and self-assembly techniques, in this paper we try to synthesize porous silica-montmorillonite heterostructured materials, starting with natural sodium montmorillonite which are ubiquitous so their cost effectiveness will continue to be lower than any synthetic competitive materials. The silica will be orderly assembled within gallery of layers, using the template-directing action. Through the catalytic alkylation reaction of catechol to produce polymerization inhibitor 4-tertbutylcatechol, the catalytic properties of porous silica-montmorillonite heterostructure were evaluated. 

A composite in general is a heterostructural material whose properties are determined by the number of different phases of the material, the volume fractions of the phases, the properties of Individual phases, and the ways in which different phases are interctm-nected [7,8). The latter is Uie most important future of composites, since the mixing rules of a given property are controlled by the self-oonnectiveness of individual phases [8). 

Heterostructured materials based on the assembly of inorganic solids of different nature are an attractive type of nanoscale architecture in which the properties of both components may be coupled in the resulting material. Moreover, the existence of interactions at the interface may result in novel properties and synergistic effects. Among the different synthetic strategies for the development of new functional heterostructured materials, the sol-gel process offers interesting possibilities that enable the development of novel nanoarchitectures mainly based on the in situ formation of diverse... 

When a stable spinel LiNio sMno 5O4 is coated on Li2Mn03 by a simple dip-and-dry method, a spinel/layered heterostructured material is prepared. This heterostructured material can maximize the inherent advantages of the 3D Lh insertion/extraction framework of the spinel structure and provides a high Li+ storage capacity in the layered structure. As shown in Figure 6.3, the heterostructured material has excellent rate capability and high capacity [9]. 

A more effective carrier confinement is offered by a double heterostructure in which a thin layer of a low-gap material is sandwiched between larger-gap layers. The physical junction between two materials of different gaps is called a heterointerface. A schematic representation of the band diagram of such a stmcture is shown in figure C2.l6.l0. The electrons, injected under forward bias across the p-n junction into the lower-bandgap material, encounter a potential barrier AE at the p-p junction which inliibits their motion away from the junction. The holes see a potential barrier of... 

Several heterostructure geometries have been developed since the 1970s to optimize laser performance. Initial homojunction lasers were advanced by the use of heterostmctures, specifically the double-heterostmcture device where two materials are used. The abiUty of the materials growth technology to precisely control layer thickness and uniformity has resulted in the development of multiquantum well lasers in which the active layer of the laser consists of one or mote thin layers to allow for improved electron and hole confinement as well as optical field confinement. 

The production of emitting sources requires further development in material technology, as the emitting wavelength is controlled by the compositions of alloy semiconductors to form heterostructures such as InGaAs/InAs" " or III-V alloy systems. 

Superhard materials implies the materials with Vickers hardness larger than 40 GPa. There are two kinds of super-hard materials one is the intrinsic superhard materials, another is nanostructured superhard coatings. Diamond is considered to be the hardest intrinsic material with a hardness of 70-100 GPa. Synthetic c-BN is another intrinsic superhard material with a hardness of about 48 GPa. As introduced in Section 2, ta-C coatings with the sp fraction of larger than 90 % show a superhardness of 60-70 GPa. A typical nanostructured superhard coating is the heterostructures or superlattices as introduced in Section 4. For example, TiN/VN superlattice coating can achieve a super-hardnessof56 GPa as the lattice period is 5.2 nm[101]. 

The creation of nanoscale sandwiches of compound semiconductor heterostructures, with gradients of chemical composition that are precisely sculpted, could produce quantum wells with appropriate properties. One can eventually think of a combined device that incorporates logic, storage, and communication for computing—based on a combination of electronic, spintronic, photonic, and optical technologies. Precise production and integrated use of many different materials will be a hallmark of future advanced device technology. 

The fundamental physical properties of nanowire materials can be improved even more to surpass their bulk counterpart using precisely engineered NW heterostructures. It has been recently demonstrated that Si/Ge/Si core/shell nanowires exhibit electron mobility surpassing that of state-of-the-art technology.46 Group III-V nitride core/shell NWs of multiple layers of epitaxial structures with atomically sharp interfaces have also been demonstrated with well-controlled and tunable optical and electronic properties.47,48 Together, the studies demonstrate that semiconductor nanowires represent one of the best-defined nanoscale building block classes, with well-controlled chemical composition, physical size, and superior electronic/optical properties, and therefore, that they are ideally suited for assembly of more complex functional systems. 

Most of the devices described up to now are based on materials that tend to crystallize [phthalocyanines, porphyrins and perylenetetracarboxydiimids, (59)] [276, 277], or form liquid crystalline phases [278, 279]. With respect to amorphous glasses, light sensitive donor-acceptor type molecules, for example, the p-type triarylamines tris [4-methylphenyl(4-nitrophenyl)ammo]triphenylamine and tris[5-(dimesitylboryl)thiophen-2-yl]triphenylamine have been combined with an n-type material in a double-layer heterostructure [280]. The cells respond to visible light from 400 to 800 nm with overall efficiencies of 0.1%. 

Shin, K.-S., et al., High quality graphene-semiconducting oxide heterostructure for inverted organicphotovoltaics. Journal of Materials Chemistry, 2012. 22(26) p. 13032-13038. 

The third family of research grade materials is less well defined and encompasses aerogels of carbon [81,82] designed mesoscopic void structures in C3 with nanostruc-tured fillers [51,83], composites with nanocarbon fillers [24,82,84 88] and carbon-heterostructure [54,89-94] compounds. The references stated here are only examples for a wide range of activities stemming from the efforts to synthesize novel nanostruc-tured composites. These materials often exhibit unusual surface properties and are used in electrochemical and catalytic applications rather in the domain of traditional C3 compounds where mechanical properties dominate the application profile. 

Figure 7. Difference in the spontaneous emission enhancement in a LED (a) and a microcavity laser (b) Density of electronic states in bulk semiconductor material and lowdimensional semiconductor heterostructures (c).

Clearly, to increase the enhancement factor, it is necessary to design and fabricate high-Q, small-V microresonators. However, cavity-enhanced LEDs based on the microresonators with high-Q modes must have equally narrow material spontaneous emission linewidths (Fig. 7a), which are not easily realized in bulk or heterostructure quantum-well microresonators. The recently proposed concept of an active material system, semiconductor quantum dots (QDs) (Arakawa, 2002) combines the narrow linewidth... 

We now deal with the structures that molecules build on substrate surfaces at full coverage, that is in the ML regime. Such hybrid systems are known as heterostructures. H. Kroemer dehned heterostructures as heterogeneous semiconductor structures built from two or more different semiconductors, in such a way that the transition region or interface between the different materials plays an essential role in any device action (Kroemer, 2001). The term heterostructure can be generalized to any... 

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