Biopolymer-Polysiloxane Double Network Aerogels

A new series of transparent aerogels of biopolymer-polysiloxane double networks is reported. Biopolymer aerogels have attracted much attention from green and sustainable aspects but suffered from strong hydrophilicity and difficulty to make homogeneous structures in nanoscale; these drawbacks are overcome by compositing with a polysiloxane network. Alginate-polymethylsilsesquioxane aerogel has high optical transparency, water repellency, comparable superinsulation property and improved bending flexibility compared to pure polymethylsilsesquioxane aerogel. The nanoscale homogeneity is realized by separating the crosslinking steps for two networks in a sequential protocol: condensation of siloxane bonds and metal-crosslinking of biopolymer. The crosslinking order, biopolymer-first or siloxane-first, and universality/limitation of biopolymer-crosslinker pairs are discussed to construct fundamental chemistry of double network systems for their further application potentials.     

3D hierarchical MnO2 aerogels with superhydrophobicity for selective oil–water separation

Inorganic nanowire aerogel with low density, high specific surface area and high porosity has received increasing attention in the field of materials physics and chemistry because of not only the unique structural and physical features of metallic oxide but also low cost, environmental friendliness and earth abundant of precursor materials. In this work, MnO₂ nanowire aerogels (MNA) with ultralow density, and stable 3D hierarchical structures was successfully fabricated by freeze‐drying processes using MnO₂ nanowire as building blocks. The length of MnO₂ nanowires exceeds 100 μm, making it easier to cross‐link and self‐assemble into a 3D network of aerogels, and the acid and alkali resistance of MnO₂ enables it to adapt to extreme environments. Simultaneously, the monodispersed MnO₂ nanowire was prepared by the hydrothermal method, followed by acid treatment. To obtain superhydrophobic properties and achieve selective oil adsorption, the surfaces of nanowire aerogels were grafted the hydrophobic groups with low surface energy via vapor deposition. It is indicated that the obtained 3D hierarchical MNA show both superhydrophobic and super‐lipophilic properties simultaneously with a high‐water contact angle of 156°  ±  2° and an oil contact angle of 0°. And the MNA exhibited a high oil adsorption capacity of 85–140 g/g, thereby indicating its potential applications in oil/water separation. More importantly, the resulting MNA can be recycled ten cycles without loss of oil absorption capacity (more than 120 g/g). The results presented in this work demonstrate that the as‐prepared nanowire aerogel may find applications in chemical separation and environmental remediation for large‐scale absorption of oils from water.     

Strong,Thermally Superinsulating Biopolymer–Silica Aerogel Hybrids by Cogelation of Silicic Acid with Pectin

Silica aerogels are excellent thermal insulators, but their brittle nature has prevented widespread application. To overcome these mechanical limitations, silica–biopolymer hybrids are a promising alternative. A one‐pot process to monolithic, superinsulating pectin–silica hybrid aerogels is presented. Their structural and physical properties can be tuned by adjusting the gelation pH and pectin concentration. Hybrid aerogels made at pH 1.5 exhibit minimal dust release and vastly improved mechanical properties while remaining excellent thermal insulators. The change in the mechanical properties is directly linked to the observed “neck‐free” nanoscale network structure with thicker struts. Such a design is superior to “neck‐limited”, classical inorganic aerogels. This new class of materials opens up new perspectives for novel silica–biopolymer nanocomposite aerogels.     

Strong,Thermally Superinsulating Biopolymer–Silica Aerogel Hybrids by Cogelation of Silicic Acid with Pectin

Silica aerogels are excellent thermal insulators, but their brittle nature has prevented widespread application. To overcome these mechanical limitations, silica–biopolymer hybrids are a promising alternative. A one‐pot process to monolithic, superinsulating pectin–silica hybrid aerogels is presented. Their structural and physical properties can be tuned by adjusting the gelation pH and pectin concentration. Hybrid aerogels made at pH 1.5 exhibit minimal dust release and vastly improved mechanical properties while remaining excellent thermal insulators. The change in the mechanical properties is directly linked to the observed “neck‐free” nanoscale network structure with thicker struts. Such a design is superior to “neck‐limited”, classical inorganic aerogels. This new class of materials opens up new perspectives for novel silica–biopolymer nanocomposite aerogels.     

One-pot synthesis,characterization and properties of acid-catalyzed resorcinol/formaldehyde cross-linked silica aerogels and their conversion to hierarchical porous carbon monoliths

A rapid and facile synthesis of resorcinol/formaldehyde cross-linked silica (RF/SiO₂) aerogels was carried out in one pot based on an acid-catalyzed route, instead of the previously reported base-catalyzed ones. The gelation time was reduced to several hours at room temperature while it took several days even under heating conditions in the base-catalyzed ones. The interpenetrating network of RF/SiO₂ aerogels showed similar porous structures with those of silica aerogels or RF aerogels. Their thermal conductivity was as low as that of the typical glass wool materials. The mechanical properties are characterized by dynamic mechanical analysis and compression testing. At room temperature, the results of compression testing show that the compressive Young’s modulus or ultimate failure strength of RF/SiO₂ aerogel specimen is higher than that of native SiO₂ aerogels with a similar density. The one-pot method improves the efficiency and reduces the cost of RF/SiO₂ aerogels. The hierarchical porous carbon monoliths are also converted from carbonized RF/SiO₂ aerogels by an additional HF treatment. Hence, they could be further explored as multifunctional candidate materials for thermal, mechanical, and electrochemical applications.     

Progress on the Structures and Functions of Aerogels

Aerogel materials possess a wide variety of excellent functions,hence a striking number of applications have developed for them.In this paper,we present a historic review of the aerogel materials,showing the main concepts,research methods,important scientific problems,formation mechanism,structure characteristics and essence of aerogel.More applications are evolving as the scientific and engineering community,which becomes familiar with the unusual and exceptional physical properties of aerogels.In addition,we also discuss the huge development potential and prospect of polysaccharide aerogels as the research trend in the future.     

Characterization of the microstructures of copper-based aerogels on the sol–gel process

In this thesis, we will elaborate on the sol–gel process during the preparation of monolithic copper-based aerogel. The microstructure of the copper-based aerogel appears to be various due to the different amounts of raw materials, such as polyacrylic acid, propene oxide, deionized water (H₂O) and copper(II) chloride (CuCl₂) in the sol–gel process. The proper molar ratios between these reactants play a crucial factor in mediating the morphology of the aerogel. The aerogels are characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy and Brunauer–Emmett–Teller methods. The combined results indicate that the copper-based aerogel shows a typical three-dimensional porous structure with a large surface areas about 568 m²/g, and the skeleton structure of the aerogel is composed of a large number of primary particles with the size about a few nanometers.     

Foam-like materials based on whey protein isolate

Low density materials from sustainable whey protein were fabricated through a simple, environmentally-friendly freeze-drying process. Aerogels produced solely from whey protein show poor mechanical properties, consistent with those of films produced from that biopolymer. The compressive moduli of these lamellar materials were increased by more than an order of magnitude by crosslinking, and further increased with increasing aerogel densities. Blending whey protein with alginate allowed for the production of bio-based aerogels with higher mechanical properties than those produced with whey alone, though thermal properties were slightly decreased by blending.     

Alumina aerogels prepared via rapid supercritical extraction

Alumina aerogels with surface areas from 460 to 840 m²/g and bulk densities from 0.025 to 0.079 g/cm³ were successfully fabricated using variations of an aluminum isopropoxide-based recipe developed by Armor and Carlson and the rapid supercritical extraction (RSCE) process developed at Union College. By utilizing the Union College RSCE method, it is possible to convert an alumina aerogel precursor mixture into aerogel monoliths in as little as 7.5 h. This process is safer than methanol extraction in an autoclave and faster and simpler than liquid CO₂ solvent exchange and extraction. By increasing the concentration of aqueous HNO₃ used in the precursor mixture, we were able to fabricate aerogels with significantly increased surface area, decreased bulk density, and altered microstructure. We attribute the observed variation in these aerogel properties at a given HNO₃ concentration to environmental factors such as humidity. The ability to more easily fabricate alumina aerogels with desirable properties will assist in making them a viable option for catalytic and other applications.     

Development of Ferroelectric Aerogels

For ultrasonic applications in gases porous piezoelectric transducers with low acoustic impedances are required. Highly porous piezoceramics can be prepared by sol-gel processing, supercritical drying and subsequent firing. These PT and PZT aerogels are obtainable as crystalline monoliths with porosities up to 70 vol%. In this paper the influence of sol-gel-synthesis, stoichiometry, drying conditions and heat treatment on the material properties are reviewed.Lowering the coercive field strength by dopants is necessary in order to facilitate the polarization of highly porous PZT-ceramics. New results show that the introduction of 2 mol% neodymium is possible in the sol-gel synthesis of the aerogel precursor. Most structural properties of the resulting PbNd_0.02Zr_0.53Ti_0.47O₃ aerogels are similar to those of the undoped material.     

Wettability study of surface modified silica aerogels with different silylating agents

In wettability study, surface free energy interactions are of crucial importance for silica aerogels in which absorption of organic liquids and transportation of chemicals carried out for chemical and biotechnological applications. In present study, we have used Lifshitz–van der Waals/acid–base approach for calculation of surface free energy of aerogel sample. We have investigated that the surface free energy values of aerogels are 45.95, 51.42 and 45.69 mJ/m² by modifying their surfaces using 7 % chlorotrimethylsilane (TMCS), dimethyldichlorosilane (DMDCS) and hexamethyldisilazane (HMDZ) silylating reagents with solvent, respectively. The alcogels were prepared by two step acid–base catalyzed process where the molar ratio of precursors tetraethoxysilane:methanol:oxalic acid:NH₄OH:NH₄F was kept at optimal value of 1:16.5:0.71:0.58:0.60:0.98, respectively. To modify gel surfaces, TMCS, DMDCS and HMDZ concentration have been varied from 5 to 12 % and such alcogels were dried at ambient pressure. The aerogels have been characterized by fourier transform infrared spectroscopy, scanning electron microscopy, thermo-gravimetric and differential thermal analysis and Wetting properties of silica aerogel surfaces was studied by contact angle measurements. The surface chemical composition of DMDCS modified silica aerogels was studied by using X-ray photoelectron spectroscopy. As there is not any direct method, we have used Lifshitz–van der Waals/acid–base approach which gives, polar and non-polar components of aerogels surface free energy.     

Hydrophobic Silica Aerogels Strengthened with Nonwoven Fibers

Hydrophobic silica aerogels were prepared via a sol‐gel process by surface modification at ambient pressure. Nonwoven fibers were distributed inside the silica aerogels as a composite to act as a supporting skeleton which increased the mechanical property of the silica aerogels. The morphology and pore structure of the composites were characterized by scanning electron microscopy (SEM) and N₂ adsorption analyzer. The contact angle and the adsorption capacities of the composites were also determined. The results show that silica aerogels dispersed uniformly and maintained high porosity in the aerogel‐fiber composites. They have excellent hydrophobic properties and are excellent adsorptive materials.     

Polyurea based aerogel for a high performance thermal insulation material

Less fragile lightweight nanostructured polyurea based organic aerogels were prepared via a simple sol–gel processing and supercritical drying method. The uniform polyurea wet gels were first prepared at room temperature and atmospheric pressure by reacting different isocyanates with polyamines using a tertiary amine (triethylamine) catalyst. Gelation kinetics, uniformity of wet gel, and properties of aerogel products were significantly affected by both target density (i.e., solid content) and equivalent weight (EW) ratio of the isocyanate resin and polyamine hardener. A supercritical carbon dioxide (CO₂) drying method was used to extract solvent from wet polyurea gels to afford nanoporous aerogels. The thermal conductivity values of polyurea based aerogel were measured at pressures from ambient to 0.075 torr and at temperatures from room temperature to −120 °C under a pressure of 8 torr. The polyurea based aerogel samples demonstrated high porosities, low thermal conductivity values, hydrophobicity properties, relatively high thermal decomposition temperature (~270 °C) and low degassing property and were less dusty than silica aerogels. We found that the low thermal conductivities of polyurea based aerogels were associated with their small pore sizes. These polyurea based aerogels are very promising candidates for cryogenic insulation applications and as a thermal insulation component of spacesuits.     

Elastic organic–inorganic hybrid aerogels and xerogels

Novel aerogels and xerogels with methylsilsesquioxane (MSQ, CH₃SiO_1.5) networks have been prepared by a modified sol–gel process using surfactant and urea as a phase-separation inhibitor and as an accelerator for the condensation reaction, respectively. Optimized aerogels dried under a supercritical condition not only showed the similar properties as conventional pure silica aerogels such as high transparency and porosity etc, but also demonstrated outstanding mechanical strength against compression; the aerogel drastically shrank upon loading and then recovered when unloaded, which is called a “spring-back” behavior. On ambient pressure drying, the wet gel also exhibited the similar response against compression stress originated from the capillary pressure, and thus xerogels with the comparative structure and properties to those of corresponding aerogels have also been obtained. This unusual mechanical behavior is attributed to the trifunctional flexible networks of MSQ, low silanol concentration which prevents the irreversible shrinkage, and high concentration of a hydrophobic methyl group directly attached to every silicon atom which helps re-expansion after the temporal shrinkage.     

Synthesis monolithic copper-based aerogel with polyacrylic acid as template

Copper-based monolithic aerogel was prepared by sol?Cgel method with inorganic salt as precursor, the polyacrylic acid as template and the propylene oxide as gelation agent. The as-prepared aerogel was calcined at 400?°C to remove the organic substances and obtain crystalline copper-oxide nanostructured materials (tenorite, JCPDS File No. 00-045-0937). The aerogels?? structural properties were characterized by the field emission scanning electron microscopy, the high resolution transmission electron microscopy, the X-ray diffraction (XRD), and the Brunauer-Emmett-Teller methods. The results indicate that the as-prepared copper-based aerogel shows a typical three-dimensional porous structure with a large surface areas about 587?m²/g. The XRD patterns show that the as-prepared copper-based aerogel belongs to amorphous materials. The phase transition from the amorphous to crystalline copper oxide occurs at 400?°C.     

Optically transparent silica aerogels based on sodium silicate by a two step sol–gel process and ambient pressure drying

Interest in improving the optical transmission of sodium silicate-based aerogels by ambient pressure drying led to the synthesis of aerogels using a two-step sol–gel process. To produce optically transparent silica aerogel granules, NH₄F (1 M) and HCl (4 M) were used as hydrolyzing and condensation catalysts, respectively. The silica aerogels were characterized by their bulk density, porosity (%), contact angle and thermal conductivity. Optical transmission of as synthesized aerogels was studied by comparing the photos of aerogel granules. Scanning electron microscopic study showed the presence of fractal structures in these aerogels. The degree of transparency in two step sol–gel process-based aerogels is higher than the conventional single step aerogels. The N₂ adsorption–desorption analysis depicts that the two step sol–gel based aerogels have large surface areas. Optically transparent silica aerogels with a low density of ∼0.125 g/cc, low thermal conductivity of ∼0.128 W/mK and higher Brunauer, Emmett, and Teller surface area of ∼425 m²/g were obtained by using NH₄F (1 M), HCl (4 M), and a molar ratio of Na₂SiO₃::H₂O::trimethylchlorosilane of 1::146.67::9.46. The aerogels retained their hydrophobicity up to 500 °C.     

An Easy Way To Prepare Monolithic Inorganic Oxide Aerogels

Inorganic oxide aerogels have unique thermal, optical, electrical, magnetic, and chemical properties, which result in them potentially having a broad range of applications. However, their preparation is commonly based on a supercritical drying method, which greatly limits real applications of aerogels and their commercialization. Here we demonstrate a general method for drying wet gels to form aerogels that is based on the sublimation of organic solvent. The organic solvent must have a low surface tension, undergo sublimation easily, and have a high freezing point to allow the rapid synthesis of monolithic inorganic oxide aerogels under vacuum conditions. This cost‐effective process will facilitate application of aerogel materials. This approach may also be used for the preparation of other porous materials, whose theoretical and practical applications should be investigated.     

Heat-Treated Aerogel as a Catalyst for the Oxygen Reduction Reaction

Aerogels are fascinating materials that can be used for a wide range of applications, one of which is electrocatalysis of the important oxygen reduction reaction. In their inorganic form, aerogels can have ultrahigh catalytic site density, high surface area, and tunable physical properties and chemical structures—important features in heterogeneous catalysis. Herein, we report on the synthesis and electrocatalytic properties of an iron–porphyrin aerogel. 5,10,15,20-(Tetra-4-aminophenyl)porphyrin (H₂TAPP) and Fe^II were used as building blocks of the aerogel, which was later heat-treated at 600 °C to enhance electronic conductivity and catalytic activity, while preserving its macrostructure. The resulting material has a very high concentration of atomically dispersed catalytic sites (9.7×10²⁰ sites g⁻¹) capable of catalyzing the oxygen reduction reaction in alkaline solution (E_onset=0.92 V vs. RHE, TOF=0.25 e⁻ site⁻¹ s⁻¹ at 0.80 V vs. RHE).     

Heat‐Treated Aerogel as a Catalyst for the Oxygen Reduction Reaction

Aerogels are fascinating materials that can be used for a wide range of applications, one of which is electrocatalysis of the important oxygen reduction reaction. In their inorganic form, aerogels can have ultrahigh catalytic site density, high surface area, and tunable physical properties and chemical structures—important features in heterogeneous catalysis. Herein, we report on the synthesis and electrocatalytic properties of an iron–porphyrin aerogel. 5,10,15,20‐(Tetra‐4‐aminophenyl)porphyrin (H₂TAPP) and Fe^II were used as building blocks of the aerogel, which was later heat‐treated at 600 °C to enhance electronic conductivity and catalytic activity, while preserving its macrostructure. The resulting material has a very high concentration of atomically dispersed catalytic sites (9.7×10²⁰ sites g^?1) capable of catalyzing the oxygen reduction reaction in alkaline solution (E_onset=0.92 V vs. RHE, TOF=0.25 e^? site^?1 s^?1 at 0.80 V vs. RHE).     

Structure and properties of polyimide aerogels with different skeleton flexibilities

ABSTRACT

In order to better understand the influences of polyimide (PI) skeleton structure and freeze-drying process on the properties of PI aerogel materials, PI molecular chains (ODPA-ODA, BPDA-ODA, BPDA-PPDA) with different stiffnesses and flexibilities were designed and a series of PI aerogels were accordingly fabricated by freeze-drying technique. The aerogels produced featured light weight (density of 0.01–0.16 g/cm³) and high flexibility, and their density, pore structure, and compress recovery performance could be well controlled by delicately tuning the molecular chain structure and solid contents of the poly (amic acid) salt solution. In addition, a hard PI aerogel with enhanced compressive strength was obtained by quick-freezing in liquid nitrogen.