Due to their various applications, metal oxides are of high interest for fundamental research and commercial usage. Per applications as catalysts or electrochemical devices, the tailored design of metal oxides featuring a high specific surface area and additional functionalities is of the utmost importance for the performance of the resulting materials. We report a new method for preparing free-standing films consisting of hierarchically porous metal oxides (titanium and niobium based) by combining emulsion polymerization and shear-induced monodisperse particle self-assembly in the presence of sol−gel precursors. After thermal treatment, the resulting porous materials can be used as electrodes in Li-ion batteries. The titanium and niobium sol−gel precursors were partially immobilized to the surface of organic core−interlayer particles featuring hydroxyl groups to obtain hybrid organic− inorganic particles through the melt−shear organization process. Free-standing particle-based films, in analogy to elastomeric opal films and colloidal crystals, can be prepared in a convenient one-step preparation process. After thermal treatment, ordered pores are obtained, while the pristine metal oxide precursor shell can be converted to the (mixed) metal oxide matrix. Heat treatment under CO 2 leads to mixed-TiNb oxide/carbon hybrid materials. The highly porous derivative structure enhances electrolyte permeation. When tested as Li-ion battery electrodes, it shows a specific capacity of 335 mAh•g −1 at a rate of 10 mA•g −1 . After 1000 cycles at 250 mA•g −1 , the electrodes still provided a specific capacity of 191 mAh•g −1 .

The preparation of ordered macroporous SiCN ceramics has attracted significant interest and is an attractive area for various applications, e.g., in the fields of catalysis, gas adsorption, or membranes. Non-oxidic ceramics, such as SiCN, own a great stability based on the covalent bonds between the containing elements, which leads to interesting properties concerning resistance and stability at high temperature. Their peculiar properties have become more and more important for a manifold of applications, like catalysis or separation processes, at high temperatures. Within this work, a feasible approach for the preparation of ordered porous materials by taking advantage of polymer-derived ceramics is presented. To gain access to free-standing films consisting of porous ceramic materials, the combination of monodisperse organic polymer-based colloids with diameters of 130 nm and 180 nm featuring a processable preceramic polymer is essential. For this purpose, the tailored design of hybrid organic/inorganic particles featuring anchoring sites for a preceramic polymer in the soft shell material is developed. Moreover, polymer-based core particles are used as sacrificial template for the generation of pores, while the preceramic shell polymer can be converted to the ceramic matrix after thermal treatment. Two different routes for the polymer particles, which can be obtained by emulsion polymerization, are followed for covalently linking the preceramic polysilazane Durazane1800 (Merck, Germany): (i) Free radical polymerization and (ii) atom transfer radical polymerization (ATRP) conditions. These hybrid hard core/soft shell particles can be processed via the so-called melt-shear organization for the one-step preparation of free-standing particle films. A major advantage of this technique is the absence of any solvent or dispersion medium, enabling the core particles to merge into ordered particle stacks based on the soft preceramic shell. Subsequent ceramization of the colloidal crystal films leads to core particle degradation and transformation into porous ceramics with ceramic yields of 18–54%.

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Opal films with their vivid structural colors represent a field of tremendous interest and obtained materials offer the possibility for many applications, such as optical sensors or anti-counterfeiting materials. A convenient method for the generation of opal structures relies on the tailored design of core-interlayer-shell (CIS) particles. Within the present study, elastomeric opal films were combined with stimuli-responsive photoacids to further influence the optical properties of structurally colored materials. Starting from cross-linked polystyrene (PS) core particles featuring a hydroxy-rich and polar soft shell, opal films were prepared by application of the melt-shear organization technique. The photoacid tris(2,2,2-trifluoroethyl) 8-hydroxypyrene-1,3,6-trisulfonate (TFEHTS) could be conveniently incorporated during freeze-drying the particle dispersion and prior to the melt-shear organization. Furthermore, the polar opal matrix featuring hydroxylic moieties enabled excited-state proton transfer (ESPT), which is proved by spectroscopic evaluation. Finally, the influence of the photoacid on the optical properties of the 3-dimensional colloidal crystals were investigated within different experimental conditions. The angle dependence of the emission spectra unambiguously shows the selective suppression of the photoacid’s fluorescence in its deprotonated state.

Chemistry, geometric shape and swelling behavior are the key parameters that determine any successful use of man-made polymeric networks (gels). While understanding of the swelling behavior of both water-swellable hydrogels and organogels that swell in organic solvents can be considered well-advanced with respect to fossil fuel-based polymer networks, the understanding, in particular, of wood-derived polymers in such a network architecture is still lacking. In this work, we focus on organogels derived from hydroxypropyl cellulose (HPC) ester. The latter polymer was functionalized with saturated and unsaturated fatty acids, respectively. Due to their tailored chemical constitution, we demonstrated that such polysaccharide can be crosslinked and simultaneously surface-bound by using a photo-induced radical reaction using a photo-initiator. Based on the choice of fatty acid used in the design of the HPC ester, and by controlling the degree of substitution (DS) obtained during the esterification of the polysaccharide, modular manipulation of the physical properties (e.g., polarity) of the resulting gel is possible. Depending on the initiator employed, different wavelengths of light, from UV to visible, can be utilized for the crosslinking reaction, which facilitates the deployment of a range of light sources and different lithographic methods. Additionally, we showed that altering of the illumination time allows to tailor the netpoint density, and thus, the degree of linear deformation in equilibrium and the swelling kinetics. Finally, we performed a proof-of-principle experiment to demonstrate the application of our material for the generation of spatially resolved polymer patches to enrich organic molecules from a solution within a microfluidic channel.