Metal alkoxides of the type (R'0)"E-X-A, where A represents a functional organic group, and X is a hydrolytically stable spacer linking A and the metal alkoxide moiety E(OR' )", are interesting precursors for the preparation of novel materials composed of both inorganic and organic entities. The basic chemistry behind the preparation and the sol-gel processing of these compounds is reviewed. The manifold options for chemical modification of both the inorganic and the organic groups allow the deliberate preparation of materials with special properties. Selected materials syntheses are discussed to demonstrate the scope of possible applications.

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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.

Air, air, air…︁ and some solid skeleton; this is the basis for an interesting class of materials-the aerogels (shown schematically on the right). Can one therefore speak of "simple" chemistry? The design of such a filigrane network requires the very careful control of chemical parameters. The reward is an assortment of different property profiles owing to the richness of possible variations.

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.

Due to the synergic feature of individual components in hybrid (nano)biomaterials, their application in regenerative medicine has drawn significant attention. Aiming to address all the current challenges of aerogel as a potent scaffold in bone tissue engineering application, we adopted a novel synthesis approach to synergistically improve the pore size regime and mechanical strength in the aerogel. The three-dimensional aerogel scaffold in this study has been synthesized through a versatile one-pot aqueous-based sol−gel hybridization/assembly of organosilane (tetraethyl orthosilicate) and silk fibroin (SF) biopolymer, followed by unidirectional freeze-casting of the as-prepared hybrid gel and supercritical drying. The developed ultralight silica-SF aerogel hybrids demonstrated a hierarchically organized porous structure with interesting honeycomb-shaped micromorphology and microstructural alignment (anisotropy) in varied length scales. The average macropore size of the hybrid aerogel lied in ∼0.5−18 μm and was systematically controlled with freeze-casting conditions. Together with high porosity (91−94%), high Young's modulus (∼4−7 MPa, >3 order of magnitude improvement compared to their pristine aerogel counterparts), and bone-type anisotropy in the mechanical compressive behavior, the silica-SF hybrid aerogel of this study acted as a very competent scaffold for bone tissue formation. The results of in vitro assessments revealed that the silica-SF aerogel is not only cytocompatible and nonhemolytic but also acted as an open porous microenvironment to trigger osteoblast cell attachment, growth, and proliferation on its surface within 14 days of incubation. Moreover, to support the in vitro results, in vivo bone formation within the aerogel implant in the bone defect site was studied. The X-ray radiology and microcomputed tomography analyses confirmed that a significant new bone tissue density formed in the defect site within 25 days of implantation. Also, in vivo toxicology studies showed a zero-toxic impact of the aerogel implant on the blood biochemical and hematological parameters. Finally, the study clearly shows the potential of aerogel as a bioactive and osteoconductive open porous cellular matrix for a successful osseointegration process.

Silica monoliths exhibiting a unique hierarchical network structure with a bimodal pore size distribution and high surface areas were prepared from three different glycol-modified silanes by sol−gel processing. Tetrakis(2-hydroxyethyl)-, tetrakis(2-hydroxypropyl)-, and tetrakis(2,3-dihydroxypropyl)orthosilicate were obtained by transesterification reaction from tetraethylorthosilicate and the corresponding alcohols. The present work shows that, for ethylene glycol- and propane-1,2-diol-modified silanes, simply the release of the corresponding diols during sol−gel processing in the presence of block copolymeric surfactants such as Pluronic P123 results in phase separation on different levels. In addition to an extraordinary cellular network structure with interconnected macropores of several hundreds of nanometers in diameter, the material exhibits a well-ordered mesostructure with periodically arranged mesopores of about 6−7 nm in diameter. Interestingly, the application of glycerol-modified silanes at the given synthesis conditions results in the formation of a disordered silica mesostructure. The architectural properties and the morphology of the gel network cannot only be controlled by the choice of the glycol but also by the amount of acid catalyst in the starting composition.

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