Monolithic porous magnesium silicide.

Macroporous magnesium silicide monoliths were successfully prepared by a two-step synthesis procedure. The reaction of gaseous magnesium vapor with macro-/mesoporous silicon, which was generated from hierarchically organized meso-/macroporous silica by a magnesiothermic reduction reaction, resulted in monolithic magnesium silicide with a cellular, open macroporous structure. By adjusting the reaction conditions, such as experimental set-up, temperature and time, challenges namely loss of porosity or phase purity of Mg2Si were addressed and monolithic magnesium silicide with a cellular network builtup was obtained.

Flexible organofunctional aerogels.

Flexible inorganic-organic silica aerogels based on methyltrimethoxysilane (MTMS, CH3Si(OCH3)3) can overcome the drawbacks of conventional silica aerogels by introducing high mechanical strength, elastic recovery and hydrophobicity to monolithic materials. In this work, MTMS is co-condensed with organofunctional alkoxysilanes RSi(OMe)3 (R = vinyl, chloropropyl, mercaptopropyl, methacryloxypropyl, etc.) yielding aerogels that are not only flexible but also contain reactive functional groups. Sol-gel parameters, such as the MTMS/RSi(OMe)3 ratio, have been systematically investigated in terms of gelation behavior, complete/incomplete incorporation of the functional organic groups (confirmed by FTIR-ATR and Raman spectroscopy) and flexibility of the resulting gel. Sterically more demanding functional moieties lead to macroscopic phase separation; however, this problem was overcome by the employment of surfactants. Functional aerogels dried by supercritical extraction with carbon dioxide showed promising results in uniaxial compression tests and had an elastic recovery up to 60%. Furthermore, the accessibility of the functional groups was demonstrated by simple reactions, e.g. conversion of the chloro into azido groups via a nucleophilic substitution reaction with NaN3 followed by click reactions.

Sol-gel synthesis of monolithic materials with hierarchical porosity.

The development of synthetic routes to hierarchically organized porous materials containing multiple, discrete sets of pores having disparate length scales is of high interest for a wide range of applications. One possible route towards the formation of multilevel porous architectures relies on the processing of condensable, network forming precursors (sol-gel processes) in the presence of molecular porogens, lyotropic mesophases, supramolecular architectures, emulsions, organic polymers, or ice. In this review the focus is on sol-gel processing of inorganic and organic precursors with concurrently occurring microscopic and/or macroscopic phase separation for the formation of self-supporting monoliths. The potential and the limitations of the solution-based approaches is presented with special emphasis to recent examples of hierarchically organized silica, metal oxides and phosphates as well as carbon monoliths.

Stable carboxylic acid derivatized alkoxy silanes.

A convenient and straightforward one-pot hydrosilylation reaction of different unsaturated carboxylic acids with trialkoxysilanes in the presence of catalytic amounts of platinum(IV) dioxide resulted in excellent yields in organofunctional silanes combining carboxy- and alkoxy groups within one molecule.

High surface area crystalline titanium dioxide: potential and limits in electrochemical energy storage and catalysis.

Titanium dioxide is one of the most intensely studied oxides due to its interesting electrochemical and photocatalytic properties and it is widely applied, for example in photocatalysis, electrochemical energy storage, in white pigments, as support in catalysis, etc. Common synthesis methods of titanium dioxide typically require a high temperature step to crystallize the amorphous material into one of the polymorphs of titania, e.g. anatase, brookite and rutile, thus resulting in larger particles and mostly non-porous materials. Only recently, low temperature solution-based protocols gave access to crystalline titania with higher degree of control over the formed polymorph and its intra- or interparticle porosity. The present work critically reviews the formation of crystalline nanoscale titania particles via solution-based approaches without thermal treatment, with special focus on the resulting polymorphs, crystal morphology, surface area, and particle dimensions. Special emphasis is given to sol-gel processes via glycolated precursor molecules as well as the miniemulsion technique. The functional properties of these materials and the differences to chemically identical, non-porous materials are illustrated using heterogeneous catalysis and electrochemical energy storage (battery materials) as example.

In situ SAXS study on cationic and non-ionic surfactant liquid crystals using synchrotron radiation.

In situ synchrotron small-angle X-ray scattering was used to investigate various surfactant/water systems with hexagonal and lamellar structures regarding their structural behaviour upon heating and cooling. Measurements of the non-ionic surfactant Triton X-45 (polyethylene glycol 4-tert-octylphenyl ether) at different surfactant concentrations show an alignment of the lamellar liquid-crystalline structure close to the wall of the glass capillaries and also a decrease in d-spacing following subsequent heating/cooling cycles. Additionally, samples were subjected to a weak magnetic field (0.3-0.7 T) during heating and cooling, but no influence of the magnetic field was observed.

Incorporation of chromium carbenes in a silica matrix by sol-gel processing: application to aminolysis of alkoxycarbene complexes

Chromium carbene complexes have been immobilized in a silica matrix by sol-gel processing based on the polycondensation of (trialkoxy)silylethylphosphane ligands and tetraalkoxysilanes. The microstructure of the material obtained depends on the gelation conditions. In situ gelation of alkoxy- or aminocarbene complexes with tetramethoxysilane (TMOS) affords mesoporous materials with a homogeneous distribution of the metal complex. The metal carbene moiety is accessible for small substrates as demonstrated for the aminolysis of the incorporated methoxy(phenyl)carbene complex which slows down with increasing bulk of the amine.