Zinc oxide in the form of nanoscale materials can be regarded as one of the most important semiconductor oxides at present. However, the question of how chemical defects influence the properties of nanoscale zinc oxide materials has seldom been addressed. In this paper, we report on the introduction of defects into nanoscale ZnO, their comprehensive analysis using a combination of techniques (powder X‐ray diffraction (PXRD), X‐ray absorption spectroscopy/extended X‐ray absorption fine structure (XAS/EXAFS), electron paramagnetic resonance (EPR), magic‐angle spinning nuclear magnetic resonance (MAS‐NMR), Fourier‐transform infrared (FTIR), UV‐vis, and photoluminescence (PL) spectroscopies coupled with ab‐initio calculations), and the investigation of correlations between the different types of defects. It is seen that defect‐rich zinc oxide can be obtained under kinetically controlled conditions of ZnO formation. This is realized by the thermolysis of molecular, organometallic precursors in which ZnO is pre‐organized on a molecular scale. It is seen that these precursors form ZnO at low temperatures far from thermodynamic equilibrium. The resulting nanocrystalline ZnO is rich in defects. Depending on conditions, ZnO of high microstructural strain, high content of oxygen vacancies, and particular content of heteroatom impurities can be obtained. It is shown how the mentioned defects influence the electronic properties of the semiconductor nanoparticles.

”Systematic errors”, namely, oxygen vacancy sites in ZnO, are the active centers for the hydrogenation of CO to give methanol. Nanocrystalline ZnO with a high density of oxygen vacancies was prepared from special organometallic precursors, and its catalytic properties for methanol synthesis were studied.

Nanocasting, the 3D-transformation of self-assembled organic nanostructures into hollow inorganic replicas under preservation of fine structural details has recently turned out to be a versatile tool, both for the synthesis of porous media with new pore topology as well as for the characterization of the assembled structures themselves. This review gives a review on recent work describing the potential and restrictions of nanocasting using surfactants, polymers, colloids as well as supramolecular tectons as porogens.

The main ability of amphiphilic molecules is to alter the energy of interfaces. They aid in the formation of various materials characterized by a high surface to volume ratio. Furthermore, amphiphiles tend to self-organize into structures of higher complexity. In the current study anionic surfactants containing a purely inorganic multinuclear head group of the polytungstate type R-[PW(11)O(39)](3-) were synthesized. Alkyl chains of different length were attached to the head group via siloxy bridges. Furthermore, the counterions could be varied. Ultimately, a heteropolyacid surfactant (H(+) as the counterion) could be prepared. The self-assembly behavior of the polyoxometalate surfactants into micelles and even lyotropic phases was studied. For instance, the formation of a phase with P6/mm symmetry containing hexagonally packed cylinders has been observed. Finally, it was possible to extend the functionality of classical amphiphiles. The polyoxometalate amphiphiles have been used for the emulsification of and, at the same time, as the initiator for the cationic polymerization of styrene. As a result, interesting organic-inorganic hybrid polymer latexes with surfaces containing heteropolyacid entities were prepared.

Sol-gel nanocasting is used to imprint the soft-matter structures of lyotropic phases of nonionic n-alkylpoly(ethylene oxide) amphiphiles ("C x E y ") into solid porous silica. Small angle X-ray scattering (SAXS), nitrogen sorption, and transmission electron microscopy (TEM) are used to investigate the dependence of the porosity on the block lengths or the block volumes, respectively. It is found that the size of the mesopores is a function of the lengths/volumes of both the alkyl chain (N A ) and the PEO block (N B ). Moreover, the materials contain a substantial degree of additional microporosity. A quantitative model is developed that relates the amphiphile organization during the nanocasting to the size of the mesopores and the microporosity. In particular, it turns out that depending on the number of EO units a fraction of the PEO chains contributes to the mesoporosity, while a significant portion leads to additional micropores. This model provides a quantitative description of the distribution of the hydrophobic and hydrophilic blocks within the lyotropic phase itself. Our findings indicate that the interface areas b 2 of single surfactant chains are a function of the block lengths, which can be described by a scaling law b 2 ∝ N A 0 16 N B 0 4 . Mixtures of chemically equivalent amphiphiles with different block ratios are studied in further detail. It is seen that every pore size between the size originating from the "parent" templates can be adjusted simply by mixing various amounts of two surfactants, proving that true mixed phases act as a template for the silica pores.