Crystals nanocrystals

Figure C2.17.1. Transmission electron micrograph of a Ti02 (anatase) nanocrystal. The mottled and unstmctured background is an amorjihous carbon support film. The nanocrystal is centred in die middle of die image. This microscopy allows for die direct imaging of die crystal stmcture, as well as the overall nanocrystal shape. This titania nanocrystal was syndiesized using die nonhydrolytic niediod outlined in [79].

In solution, nanocrystals are ideal spectroscopic samples however many of dieir most important properties can only be realized when diey are assembled into more complex stmctures. One way of building complex stmctures is to rely on die inlierent tendency for monodisperse spheres to crystallize. Figure C2.17.3 shows die hexagonal close-... 

Figure C2.17.6. Transmission electron micrograph and its Fourier transfonn for a TiC nanocrystal. High-resolution images of nanocrystals can be used to identify crystal stmctures. In tliis case, tire image of a nanocrystal of titanium carbide (right) was Fourier transfonned to produce tire pattern on tire left. From an analysis of tire spot geometry and spacing, one can detennine that tire nanocrystal is oriented witli its 11001 zone axis parallel to tire viewing direction [217].

Figure C2.17.7. Selected area electron diffraction pattern from TiC nanocrystals. Electron diffraction from fields of nanocrystals is used to detennine tire crystal stmcture of an ensemble of nanocrystals [119]. In tliis case, tliis infonnation was used to evaluate the phase of titanium carbide nanocrystals [217].

Figure C2.17.8. Powder x-ray diffraction (PXRD) from amoriDhous and nanocry stalline Ti02 nanocrystals. Powder x-ray diffraction is an important test for nanocrystal quality. In the top panel, nanoparticles of titania provide no crystalline reflections. These samples, while showing some evidence of crystallinity in TEM, have a major amoriDhous component. A similar reaction, perfonned with a crystallizing agent at high temperature, provides well defined reflections which allow the anatase phase to be clearly identified.

Unlike melting and the solid-solid phase transitions discussed in the next section, these phase changes are not reversible processes they occur because the crystal stmcture of the nanocrystal is metastable. For example, titania made in the nanophase always adopts the anatase stmcture. At higher temperatures the material spontaneously transfonns to the mtile bulk stable phase [211, 212 and 213]. The role of grain size in these metastable-stable transitions is not well established the issue is complicated by the fact that the transition is accompanied by grain growth which clouds the inteiyDretation of size-dependent data [214, 215 and 216]. In situ TEM studies, however, indicate that the surface chemistry of the nanocrystals play a cmcial role in the transition temperatures [217, 218]. 

The ability to control pressure in the laboratory environment is a powerful tool for investigating phase changes in materials. At high pressure, many solids will transfonn to denser crystal stmctures. The study of nanocrystals under high pressure, then, allows one to investigate the size dependence of the solid-solid phase transition pressures. Results from studies of both CdSe [219, 220, 221 and 222] and silicon nanocrystals [223] indicate that solid-solid phase transition pressures are elevated in smaller nanocrystals. 

Valov P M and Leiman V I 1997 Size effects in the melting and crystallization temperatures of copper chloride nanocrystals in glass JETP Lett. 66 510... 

Fig. 7. TEM picture of iron nanocrystals collected from the chamber soot nanocrystals are embedded in amorphous carbon globules. On the surface of some core crystals, a few fringes with 0.34-0.35 nm spacing suggesting the presence of graphitic layers are observed, as indicated by arrows.

On the other hand, in.the case of the nonionic surfactants C-15, NP-15 and 0-15 (the nonionic surfactant/cyclohexane system), mono-dispersed silicalite nanocrystals were obtained as shown in Fig. 1(c), 1(d) and 1(e), respectively. The X-ray diffraction patterns of the samples showed peaks corresponding to pentasile-type zeolite. The average size of the silicalite nanocrystals was approximately 120 nm. These results indicated that the ionicity of the hydrophilic groups in the surfactant molecules played an important role in the formation and crystallization processes of the silicalite nanocrystals. 

Mono-dispersed silicalite and ZSM-5 type zeolite nanocrystals with a diameter of 80-120 nm were successfully prepared in a surfactant-oil-water solution. The ionicity of the surfactants used in the preparation affected the crystallinity and structure of the silicalite crystals, and silicalite nanocrystals could he obtained when using a nonionic sur ctant. By adding an A1 source into the synthetic solution, ZSM-5 type zeolite nanocrystals with strong acid sites could be obtained. 

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