RESUMO
High-performance thermal insulators represented by aerogels are regarded as one of the most promising materials for energy savings. However, significantly low mechanical strength has been a barrier for aerogels to be utilized in various social domains such as houses, buildings, and industrial plants. Here, we report a synthetic strategy to realize highly transparent aerogels with unusually high bending flexibility based on poly(methylsilsesquioxane) (PMSQ) network. We have constructed mesoscopic fine fiber-like structures of various sizes in PMSQ gels by the combination of phase separation suppression by tetramethylammonium hydroxide (TMAOH) and mesoscopic fiber-like assembly by nonionic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-b-PPO-b-PEO) type surfactant. The optimized mesoscale structures of PMSQ gels have realized highly transparent and resilient monolithic aerogels with much high bendability compared to those reported in previous works. This work will provide a way to highly insulating materials with glasslike transparency and high mechanical flexibility.
RESUMO
Enormous efforts have been devoted to the development of crystalline aerogels toward heterogeneous catalysis, energy storage, ion/molecular absorption, and luminescence. However, properties of aerogels are not fully exploited due to their low content of functional moieties embedded in their solid networks, low crystallinity, and limited chemical compositions. Herein, we develop a one-pot approach based on crystallization from amorphous metal hydroxides modified with a ß-diketone ligand, toward crystalline transition-metal hydroxide aerogels. Synthesis of monolithic and crystalline aerogels of layered double hydroxide (LDH) was performed in a Ni-Al system starting from aqueous ethanol solutions of NiCl2·6H2O and AlCl3·6H2O with acetylacetone (acac) as an organic ligand. Propylene oxide (PO) as an alkalization reagent was added into precursory solutions to yield monolithic wet gels. The successive pH increase induces the formation of a three-dimensional (3-D) solid framework composed of amorphous Al(OH)3. Then, amphoteric Al(OH)3 undergoes crystallization into Ni-Al LDH via an acetylacetone-driven dissolution-crystallization of metal hydroxides without destroying the preformed 3-D solid framework. The process allows us to obtain crystalline aerogel monoliths with high porosity and high transparency after supercritical CO2 drying of wet gels. The present scheme can be expected to synthesize functionalized aerogel composed of crystalline transition-metal oxide/hydroxide nanobuilding blocks (NBBs).
RESUMO
The shaping of metal-organic frameworks (MOFs) has become increasingly studied over the past few years, because it represents a major bottleneck toward their further applications at a larger scale. MOF-based macroscale solids should present performances similar to those of their powder counterparts, along with adequate mechanical resistance. Three-dimensional printing is a promising technology as it allows the fast prototyping of materials at the macroscale level; however, the large amounts of added binders have a detrimental effect on the porous properties of the solids. Herein, a 3D printer was modified to prepare a variety of MOF-based solids with controlled morphologies from shear-thinning inks containing 2-hydroxyethyl cellulose. Four benchmark MOFs were tested for this purpose: HKUST-1, CPL-1, ZIF-8, and UiO-66-NH2. All solids are mechanically stable with up to 0.6 MPa of uniaxial compression and highly porous with BET specific surface areas lowered by 0 to -25%. Furthermore, these solids were applied to high-pressure hydrocarbon sorption (CH4, C2H4, and C2H6), for which they presented a consequent methane gravimetric uptake (UiO-66-NH2, ZIF-8, and HKUST-1) and a highly preferential adsorption of ethylene over ethane (CPL-1).
