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Abstract: Aerogels are porous materials but show poor mechanical properties and limited functionality, which significantly restrict their practical applications. Preparation of highly bendable and processable aerogels with multifunctionality remains a challenge. Herein we report unprecedented superflexible aerogels based on polyvinylpolydimethylsiloxane (PVPDMS) networks, PVPDMS/polyvinylpolymethylsiloxane (PVPMS) copolymer networks, and PVPDMS/PVPMS/graphene nanocomposites by a facile radical polymerization/hydrolytic polycondensation strategy and ambient pressure drying or freeze drying. The aerogels have a doubly cross‐linked organic–inorganic network structure consisting of flexible polydimethylsiloxanes and hydrocarbon chains with tunable cross‐linking density, tunable pore size and bulk density. They have a high hydrophobicity and superflexibility and combine selective absorption, efficient separation of oil and water, thermal superinsulation, and strain sensing. [ABSTRACT FROM AUTHOR]

Phase separation control is an important factor to prepare a porous monolith by an aqueous sol-gel reaction. Here, we report a surfactant-free synthesis method to obtain hydrophobic polymethylsilsesquioxane aerogels by copolymerizing a cationic-functionalized alkoxysilane N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride. The resultant materials have low-density, high visible-light transmittance, and high thermal insulating equivalent to those of prepared under the presence of surfactant. [ABSTRACT FROM AUTHOR]

Aerogels are attracting increasing attention due to their high thermal insulation ability as well as unique properties such as high porosity, surface area, and transparency. However, low mechanical strengths, originating from their unique porous structure, impede handling, formability, mass production, and extended applications. This minireview focuses on the strengthening of aerogels by several organic-inorganic hybridization strategies. In particular, successful strengthening methodologies, which employ organo-substituted alkoxysilanes as the single precursor for the sol-gel preparations, developed by the authors are highlighted. Moreover, improvements in compressive strength and elasticity lead to monolithic aerogel-like xerogels through ambient pressure drying. Correlations between structures in different length scales (e.g., molecular, network, and pore structure levels) and resultant mechanical properties are discussed for further understandings and better design toward mechanically improved aerogels/xerogels and their applications. [ABSTRACT FROM AUTHOR]

Porous polysilsesquioxane gels derived from sol–gel systems based on trifunctional silanes are reviewed. Although it is well known that trifunctional silanes possess inherent difficulties in forming homogeneous gels, increasing attention is being paid on these precursors and resultant porous polysilsesquioxanes because of hydrophobicity, functionality, and versatile mechanical properties. Much effort has been made to overcome the difficulties for homogeneous gelation, and a number of excellent porous materials with various pore properties have been explored. In this critical review, we put special emphasis on the formation of a well-defined macroporous structure by making use of phase separation, which in turn is a serious problem in obtaining homogeneous gels though. Porous polysilsesquioxane monoliths with the hierarchical structure and transparent aerogels with high mechanical durability are particularly highlighted (169 references). [ABSTRACT FROM AUTHOR]

Abstract: Detailed nanostructures have been investigated for hierarchically porous alumina aerogels and xerogels prepared from ionic precursors via sol–gel reaction. Starting from AlCl3·6H2O and poly(ethylene oxide) (PEO) dissolved in a H2O/EtOH mixed solvent, monolithic wet gels were synthesized using propylene oxide (PO) as a gelation initiator. Hierarchically porous alumina xerogels and aerogels were obtained after evaporative drying and supercritical drying, respectively. Macroporous structures are formed as a result of phase separation, while interstices between the secondary particles in the micrometer-sized gel skeletons work as mesoporous structures. Alumina xerogels exhibit considerable shrinkage during the evaporative drying process, resulting in relatively small mesopores (from 5.4 to 6.2nm) regardless of the starting composition. For shrinkage-free alumina aerogels, on the other hand, the median mesopore size changes from 13.9 to 33.1nm depending on the starting composition; the increases in PEO content and H2O/EtOH volume ratio both contribute to producing smaller mesopores. Small-angle X-ray scattering (SAXS) analysis reveals that variation of median mesopore size can be ascribed to the change in agglomeration state of primary particles. As PEO content and H2O/EtOH ratio increase, secondary particles become small, which results in relatively small mesopores. The results indicate that the agglomeration state of alumina primary particles is influenced by the presence of weakly interacting phase separation inducers such as PEO. [Copyright &y& Elsevier]

Due to the increase in the global population, industrialization, and the transition to climate neutrality through low‐emission technologies, the pressure on critical materials (CMs) continues to grow. CMs are defined as materials with a significant risk of supply chain disruption and limited substitutability. In this context, rare‐earth elements, platinum group metals, lithium, and cobalt are particularly crucial for the shift to carbon‐free economy and sustainability. One of the important strategies to endorse the goal of carbon reduction is to promote the recycling of resources. As a solution, effective recovery strategies have been developed, such as solid‐phase separation technologies based on advanced functional sorbents. This perspective article aims to provide a general assessment of the role of porous materials in closing the loop of critical materials recycling. Here, comprehensive insights are provided into recent development, design, and application of porous adsorbents commonly applied in solid‐phase extraction systems. Their current research status and problems related to their future application are also highlighted. This review covers recent advances in porous and hierarchical silica‐based materials, aerogels, covalent organic frameworks, metal–organic frameworks, and carbon‐based adsorbents. [ABSTRACT FROM AUTHOR]

Organic – inorganic hybridization strategies for the synthesis of aerogels and xerogels is discussed in the Minireview by K. Kanamori and co ‐ workers on page 5176 ff. Considerable progress in strengthened transparent aerogels and xerogels has been achieved, leading to a widening of the application range that is no longer limited to thermal superinsulation. [ABSTRACT FROM AUTHOR]

Abstract: Structure and physical properties of monolithic polymethylsilsesquioxane (PMSQ, CH3SiO1.5) aerogels have been systematically examined with varied starting compositions using a sol–gel system containing surfactant n-hexadecyltrimethylammonium chloride (CTAC). The precursor methyltrimethoxysilane (MTMS) undergoes hydrolysis and polycondensation under an acid–base two-step reaction to obtain uniform gels as a one-pot reaction. To compare the samples, each factor of starting composition, such as amount of CTAC, concentration of aqueous acetic acid solution, volume of solvent and amount of urea, is independently varied. With appropriate concentrations of surfactant CTAC, the aerogels with high light transmittance (at 550nm) are obtained, owing to the effective suppression of macroscopic phase separation. Acid–base catalysts, acetic acid and urea also impose significant effects on the properties of obtained aerogels including their molecular-level structures. The aerogel with 91% of light transmittance was obtained under an optimized condition. The lowest density of the PMSQ aerogel in this system reaches 0.045gcm−3. [Copyright &y& Elsevier]

Ambient pressure drying of polymethylsilsesquioxane gels via dynamic shrinkage-reexpansion has been investigated for preparation of aerogel-like xerogels and their application to thermal superinsulators. An extended aging of wet gels in aqueous solution containing precursor-derived species is found to be crucial in obtaining crack-free, monolithic xerogels with sufficiently low thermal conductivity (13.7 mW m − 1 K − 1 ) at bulk density of 0.140 g cm − 3 (porosity ~ 90%). [ABSTRACT FROM AUTHOR]

Abstract: A transition from hierarchical pore structures (macro- and meso-pores) to uniform mesopores in monolithic polymethylsilsesquioxane (PMSQ, CH3SiO1.5) gels has been investigated using a sol–gel system containing surfactant Pluronic F127. The precursor methyltrimethoxysilane (MTMS) undergoes an acid/base two-step reaction, in which hydrolysis and polycondensation proceed in acidic and basic aqueous media, respectively, as a one-pot reaction. Porous morphology is controlled by changing the concentration of F127. Sufficient concentrations of F127 inhibit the occurrence of micrometer-scale phase separation (spinodal decomposition) of hydrophobic PMSQ condensates and lead to well-defined mesoporous transparent aerogels with high specific pore volume as a result of the colloidal network formation in a large amount of solvent. Phase separation regulates well-defined macropores in the micrometer range on decreasing concentrations of F127. In the PMSQ-rich gelling domain formed by phase separation, the PMSQ colloidal network formation forms mesopores, leading to monolithic PMSQ gels with hierarchical macro- and meso-pore structures. Mesopores in these gels do not collapse on evaporative drying owing to the flexible networks and repulsive interactions of methyl groups in PMSQ. [Copyright &y& Elsevier]

Resilient, fire-retardant and mechanically strong polyimide-polyvinylpolymethylsiloxane (PI-PVPMS) composite aerogels have been prepared via stepwise chemical liquid deposition (SCLD). The synthesis is based on the formation of PI-PVPMS crosslinked network structure with (3-aminopropyl)trimethoxysilane (APTMS) as a coupling agent to provide reactive sites on the backbone. We successfully realize the PI in-situ growth on the whole super-flexible PVPMS gel skeleton with this simple method. The effect of APTMS amount and deposition time on the properties of final samples is deeply investigated. The resultant PI-PVPMS composite aerogels show excellent mechanical and thermal properties. They can support at least 10,000 times of their own weight and can recover 20% from a 60% of compressive strain, with an elastic modulus of 32 MPa. For thermal performance, they can maintain their structural integrity after being subjected to the alcohol lamp outer flame of around 650 °C for 30 min. These results together with the simple synthesis process demonstrate the potential for construction materials using PI-PVPMS composite aerogels. Furthermore, the SCLD synthesis method could also be applied to prepare other composite aerogels, especially for those containing complex polymer. Unlabelled Image • We successfully realize the in-situ growth of polyimide on the super-flexible PVPMS gel skeleton. • The PI-PVPMS composite aerogel shows both resilient mechanical property and high thermal stability. • The synthesis method has the potential to realize the large-scale production of PI-PVPMS composite aerogels. [ABSTRACT FROM AUTHOR]