2850 wileyonlinelibrary.com large amounts of liquids and are excellent fi lters. Sponges with a volume of 1000 cm 3 can process up to 3000 L water h −1 . Furthermore, they can conduct light as discovered recently by Brümmer et al. [ 2 ] In addition, Natalio et al. reported on the formation of sponge skeletons shown to feature great bending strength and on the role of silicatein-α in the biomineralization of silicates in sponges, which accounts for the high reversible compressibility of sponges in spite of low densities. [ 3 ] Aizenberg et al. pointed out on the example of the so-called glass sponges ( Euplectella ) the important role of the hierarchical design from the nanometer to macroscopic length scale for structural materials. [ 4 ] The structural base of sponges are multiarmed spicules of silicate or calcium carbonate, which form highly porous structures of several hierarchical layers as shown in Figure 1 A,B. This leads to highly porous ultralight 3D materials (ultralight is defi ned when the density of material is <10 mg cm −3 ).[ 5 ] In recent literature, a variety of highly porous ultralight 3D materials were reported based on carbon, ceramics, and cellulose, which were characterized by porosities >99% and relatively high compressive strength. [6][7][8][9][10] Carbon and cellulose based sponges show ultralow densities and excellent mechanical properties but soft sponges with similar mechanical integrity are missing.Since spicules of natural sponges conspicuously resemble polymer fi bers, formation of such fi brous structures by electrospinning [ 11 ] could be a promising concept for the preparation of polymer-based biomimetic analogous of natural sponges and would open the huge potential of electrospun materials for 3D sponge-type structures. Indeed, 3D porous structures were prepared by electrospinning which was nicely summarized in comprehensive review in recent literature. [ 7 ] However, previous efforts of making 3D highly porous electrospun materials, for example, via ultrasonic treatment, resulted in higher densities and correspondingly lower porosities of <99%, [ 12 ] as well as relatively poor mechanical performance. Remarkably, Eichhorn et al. claimed that theoretically ultrahigh porosities of electrospun nonwovens >99% could not be achieved. [ 13 ] In contrast to these reports, we present here the formation of ultralight weight highly porous 3D electrospun polymer fi ber-based spongy structures with densities as low as 2.7 mg cm −3 corresponding to a porosity of 99.6%. They were prepared by electrospinning of a photo cross-linkable polymer followed by UV cross-linking, mechanical cutting, suspending cut fi bers in liquid dispersion, and freezedrying. These polymer sponges showed in analogy to natural Ultralight, Soft Polymer Sponges by Self-Assembly of Short Electrospun Fibers in Colloidal DispersionsGaigai Duan , Shaohua Jiang , Valérie Jérôme , Joachim H. Wendorff , Amir Fathi , Jaqueline Uhm , Volker Altstädt , Markus Herling , Josef Breu , Ruth Freitag , Seema Agarwal , and Andreas Gre...

Microporous organically pillared layered silicates (MOPS) are a class of microporous hybrid materials that, by varying pillar density, allows for optimization of guest recognition without the need to explore different framework topologies. MOPS are found to be capable of discriminating two very similar gases, carbon dioxide and acetylene, by selective gate-opening solely through quenching pillar dynamics. Contrary to conventional gate-opening in metal organic frameworks, the additional adsorption capacity is realized without macroscopic volume changes, thus avoiding mechanical stress on the framework. Of the two gases studied, only CO can accomplish freezing of pillar dynamics. Moreover, the shape of the slit-type micropores in MOPS can easily be fine-tuned by reducing the charge density of the silicate layers. This concomitantly reduces the Coulomb attraction of cationic interlayer space and anionic host layers. Surprisingly, we found that reducing the charge density then alters the gate-opening mechanism to a conventional structural gate-opening involving an increase in volume.

A F-rich potassium hectorite, [K(0.48(2))](inter)[Mg(2.54(8))Li(0.43)](oct)[Si(4)](tet)O(10)F(2), with a layer charge of x = 0.48 per formula unit (pfu) was synthesized by high temperature melt synthesis. After Mg-exchange, the layer charge could be reduced significantly post synthesis by annealing (250 °C) as confirmed by alkylammonium exchange and cation exchange capacity. By pillaring this new low charge material with Me(2)DABCO(2+) (N,N-dimethyl-1,1-diazabicyclo [2.2.2]octane dication) and Rh(bpy)(3)(3+) (rhodium-tris-2,2'-bipyridin trication), we observed a remarkable increase in micropore volume and pore diameter by Ar/Ar(l) physisorption measurements. This method allows the tailoring of pore sizes of pillared clays by reducing the layer charge and consequently the pillar density.

One-dimensional crystalline heterostructures of two types of nanoreactors strictly alternating along the stacking direction are obtained by partial ion exchange into a synthetic clay mineral distinguished by an outstandingly homogeneous charge density. The driving force for the formation of these high interface architectures is proven to be founded in densely packed cationic molecules in the interlayer with a charge density deviating from the charge density of the host clay mineral. The established mechanism renders the approach generally applicable and will allow for synthesis of ordered heterostructures of any desired combination of functional molecules that moreover are separated by exactly 1 nm thick silicate walls. The ordered heterostructures were furthermore shown to represent the thermodynamic equilibrium suggesting the mechanism of formation to be robust.