Branched Aramid Nanofibers

Interconnectivity of components in three‐dimensional networks (3DNs) is essential for stress transfer in hydrogels, aerogels, and composites. Entanglement of nanoscale components in the network relies on weak short‐range intermolecular interactions. The intrinsic stiffness and rod‐like geometry of nanoscale components limit the cohesive energy of the physical crosslinks in 3DN materials. Nature realizes networked gels differently using components with extensive branching. Branched aramid nanofibers (BANFs) mimicking polymeric components of biological gels were synthesized to produce 3DNs with high efficiency stress transfer. Individual BANFs are flexible, with the number of branches controlled by base strength in the hydrolysis process. The extensive connectivity of the BANFs allows them to form hydro‐ and aerogel monoliths with an order of magnitude less solid content than rod‐like nanocomponents. Branching of nanofibers also leads to improved mechanics of gels and nanocomposites.     

Branched Aramid Nanofibers

Interconnectivity of components in three‐dimensional networks (3DNs) is essential for stress transfer in hydrogels, aerogels, and composites. Entanglement of nanoscale components in the network relies on weak short‐range intermolecular interactions. The intrinsic stiffness and rod‐like geometry of nanoscale components limit the cohesive energy of the physical crosslinks in 3DN materials. Nature realizes networked gels differently using components with extensive branching. Branched aramid nanofibers (BANFs) mimicking polymeric components of biological gels were synthesized to produce 3DNs with high efficiency stress transfer. Individual BANFs are flexible, with the number of branches controlled by base strength in the hydrolysis process. The extensive connectivity of the BANFs allows them to form hydro‐ and aerogel monoliths with an order of magnitude less solid content than rod‐like nanocomponents. Branching of nanofibers also leads to improved mechanics of gels and nanocomposites.     

Temperature and Composition Dependent Optical Properties of CdSe/CdS Dot/Rod-Based Aerogel Networks

Employing nanocrystals (NCs) as building blocks of porous aerogel network structures allows the conversion of NC materials into macroscopic solid structures while conserving their unique nanoscopic properties. Understanding the interplay of the network formation and its influence on these properties like size-dependent emission is a key to apply techniques for the fabrication of novel nanocrystal aerogels. In this work, CdSe/CdS dot/rod NCs possessing two different CdSe core sizes were synthesized and converted into porous aerogel network structures. Temperature-dependent steady-state and time-resolved photoluminescence measurements were performed to expand the understanding of the optical and electronic properties of these network structures generated from these two different building blocks and correlate their optical with the structural properties. These investigations reveal the influence of network formation and aerogel production on the network-forming nanocrystals. Based on the two investigated NC building blocks and their aerogel networks, mixed network structures with various ratios of the two building blocks were produced and likewise optically characterized. Since the different building blocks show diverse optical response, this technique presents a straightforward way to color-tune the resulting networks simply by choosing the building block ratio in connection with their quantum yield.     

Facile synthesis of nitrogen-doped graphene aerogels for electrochemical detection of dopamine

Nitrogen-doped graphene aerogels with three-dimensional network structures are fabricated using hydrothermal method which includes the reduction of graphene oxide by organic amine and self-assembly of reduced graphene oxide. The effect of amine-containing compounds including aniline, 2-aminoethanol, ethylenediamine, melamine and chitosan on the assembly of nitrogen-doped graphene aerogel is investigated. The microstructure and chemical composition of nitrogen-doped graphene aerogels are characterized. The results reveal that nitrogen-doped graphene aerogel prepared using aniline as nitrogen source possesses a large specific surface area, high nitrogen content, good mechanical strength and excellent electrical conductivity. Based on these features, the as-prepared nitrogen-doped graphene aerogel shows high performance in electrochemical detection of dopamine in the presence of uric acid and ascorbic acid. Given the facile and scalable processability of aerogels, the proposed nitrogen-doped graphene aerogels are expected to have potential applications in sensors and other related devices.     

Super-assembled highly compressible and flexible cellulose aerogels for methylene blue removal from water

Physical adsorption is a common method to solve the contamination of methylene blue in dyeing wastewater. As a kind of adsorption material, cellulose aerogels with high porosity and surface areas have great potential application in methylene blue removal. However, the week hydrogen bonding between cellulose nanofibers making the cellulose aerogels with the poor mechanical properties and can be easily destroyed during adsorption. Hence, the preparation of cellulose aerogels with high mechanical strength is still a great challenge. Here, we report a robust super-assembly strategy to fabricate cellulose aerogels by combining cellulose nanofibers with PVA and M-K10. The resulting cellulose aerogels not only has a robust chemically cross-linked network, but also has strong H-bonds, which greatly enhance the mechanical properties. The resulting cellulose aerogels possess a low density of 19.32 mg/cm3.Furthermore, the cellulose aerogel shows 93% shape recovery under 60% strain(9.5 k Pa under 60% strain)after 100 cycles, showing excellent mechanical property. The adsorption capacity of cellulose aerogel to methylene blue solution of 20 mg/L is 2.28 mg/g and the adsorption kinetics and adsorption isotherms have also been studied. Pseudo-second-order kinetic model and Freundlich isotherm model are more acceptable for indicating the adsorption process of methylene blue on the cellulose aerogel. Thus, this compressible and durable cellulose aerogel is a very prospective material for dyeing wastewater cleanup.     

Flammability of Polymer/Clay Aerogel Composites: An Overview

ABSTRACT

Polymer/clay aerogel composites fabricated using the freeze-drying method and water as solvent has drawn extensive attentions during the past decade. Such aerogels possess layered or network microstructures, low thermal conductivities, and good thermal stabilities; of special interest, they generally have very low flammability, which could be influenced by the composition and microstructure of the aerogel composites. The fire performance of the aerogels can be further improved with flame retardant modifications. Polymer/clay aerogel composites can also serve as effective flame retardant coatings. The mechanisms of the flame retardancy of polymer/clay aerogel composites are also discussed herein. The thorough survey of the current literatures offers useful information to realize potential of polymer/clay aerogels and help guidance to design novel high-performance polymer/clay aerogel composites.     

Carbon Nitride Aerogels for the Photoredox Conversion of Water

Aerogel structures have attracted increasing research interest in energy storage and conversion owing to their unique structural features, and a variety of materials have been engineered into aerogels, including carbon‐based materials, metal oxides, linear polymers and even metal chalcogenides. However, manufacture of aerogels from nitride‐based materials, particularly the emerging light‐weight carbon nitride (CN) semiconductors is rarely reported. Here, we develop a facile method based on self‐assembly to produce self‐supported CN aerogels, without using any cross‐linking agents. The combination of large surface area, incorporated functional groups and three‐dimensional (3D) network structure, endows the resulting freestanding aerogels with high photocatalytic activity for hydrogen evolution and H₂O₂ production under visible light irradiation. This work presents a simple colloid chemistry strategy to construct 3D CN aerogel networks that shows great potential for solar‐to‐chemical energy conversion by artificial photosynthesis.     

Polyethylene Aerogels with Combined Physical and Chemical Crosslinking: Improved Mechanical Resilience and Shape‐Memory Properties

While the introduction of polymers into aerogels strongly enhances their toughness, truly elastic monolithic aerogels which restore their dimensions upon extensive compression are still challenging to synthesize. In this context hydrophobic semi‐crystalline polymers with low glass transition temperatures, and combined stiffness and flexibility, have only recently attracted attention. Shown here is that polyethylene aerogels with a low density, and combined chemical crosslinking and high crystallinity, display high moduli and excellent mechanical resilience. To maximize the crystallinity of these aerogels while maintaining a high crosslinking density, polyethylene networks with well‐defined segments were synthesized by hydrosilylation crosslinking of telechelic, vinyl‐functionalized oligomers obtained from catalyzed chain‐growth polymerization. Recoverable deformations both above and below the melting temperature of polyethylene affords remarkable shape‐memory properties.     

化学改性氧化石墨烯交联的聚酰亚胺气凝胶

聚酰亚胺(PI)气凝胶是一类密度低、机械性能好、隔热性能优异的多孔材料, 通常使用昂贵的化学交联剂进行交联. 氧化石墨烯(GO)是近年来广受关注的用于聚合物增强的纳米功能填料. 以前报道的PI/GO 复合材料多是纤维或膜的形式. 为了获得PI/GO 复合气凝胶, 本文采用化学改性氧化石墨烯(m-GO)替代1,3,5-三(4-氨基苯氧基)苯(TAB)等常规的交联剂, 使之与4,4'-二氨基二苯基醚(ODA)和3,3',4,4'-联苯四羧酸二酐(BPDA)反应, 制得了m-GO交联的PI 气凝胶. GO的化学改性通过其与过量ODA在水热条件下反应实现. 通过扫描电子显微镜(SEM)研究了PI/m-GO气凝胶的微观结构. 分别通过氮气吸脱附测试、热重分析和热线法研究了m-GO对气凝胶的孔特性、热稳定性和热导率的影响. 测试结果表明, 所获得的PI/m-GO气凝胶保持了高的孔隙率、热稳定性和绝热性. 压缩测试结果显示, 与采用1.8% (质量分数, w)的TAB进行交联的PI 气凝胶相比,仅用0.6% (w)的m-GO交联所获得的气凝胶具有更高的比杨氏模量(杨氏模量/密度)、比屈服强度(屈服强度/密度)和更小的体积收缩率.     

氧化石墨烯功能化三聚氰胺-甲醛气凝胶涂层固相微萃取管的制备及其应用北大核心CSCD

因具有良好的萃取性能,有机气凝胶已被应用于样品前处理领域,为了进一步改善其对多环芳烃类污染物的萃取能力,利用氧化石墨烯对三聚氰胺-甲醛气凝胶进行改性,制备了一种氧化石墨烯功能化三聚氰胺-甲醛气凝胶,将其作为萃取涂层涂覆到不锈钢丝表面,通过扫描电镜和X射线光电子能谱对萃取涂层进行表征,结果表明氧化石墨烯并未破坏气凝胶的三维网络多孔结构。将4根气凝胶涂覆的不锈钢丝装进一根长度30 cm、内径0.75 mm的聚醚醚酮管内,制备了一种新型的纤维填充型固相微萃取管。将萃取管与高效液相色谱联用,构建管内固相微萃取-液相色谱在线富集分析系统。以8种多环芳烃(萘(Nap)、苊烯(Acy)、苊(Ace)、芴(Flu)、菲(Phe)、蒽(Ant)、荧蒽(Fla)和芘(Pyr))作为模型分析物,评价了萃取管的萃取性能,考察了氧化石墨烯对气凝胶萃取性能的改善,结果表明萃取效率被提升至最高2.5倍。详细考察了样品体积、样品流速、样品中有机溶剂浓度以及脱附时间对于萃取效率的影响,并建立了管内固相微萃取-液相色谱在线分析方法。该法对8种多环芳烃分析物的检出限为0.001~0.005μg/L,萘、苊烯、苊、芴的线性范围为0.017~20.0μg/L,菲、蒽的线性范围为0.010~20.0μg/L,荧蒽和芘的线性范围为0.003~15.0μg/L,精密度良好(日内重复性RSD≤4.8%,日间重复性RSD≤8.6%)。研究所发展的分析方法比已报道的某些分析方法具有更好的灵敏度、更宽的线性范围和更短的分析时间,并具有在线富集和在线分析的独特优点。将该分析方法应用于常见饮用水(包括瓶装矿泉水和饮水机的直饮水)中多环芳烃的分析检测,加标回收率试验结果(76.3%~132.8%)表明该分析方法能够高灵敏、快速、准确地检测饮用水中痕量多环芳烃污染物。经过稳定性考察,发现研究所制备的固相微萃取管在实验过程中表现出良好的使用寿命和化学稳定性。     

Nanocrystalline iron oxide aerogels as mesoporous magnetic architectures

We have developed crystalline nanoarchitectures of iron oxide that exhibit superparamagnetic behavior while still retaining the desirable bicontinuous pore-solid networks and monolithic nature of an aerogel. Iron oxide aerogels are initially produced in an X-ray-amorphous, high-surface-area form, by adapting recently established sol-gel methods using Fe(III) salts and epoxide-based proton scavengers. Controlled temperature/atmosphere treatments convert the as-prepared iron oxide aerogels into nanocrystalline forms with the inverse spinel structure. As a function of the bathing gas, treatment temperature, and treatment history, these nanocrystalline forms can be reversibly tuned to predominantly exhibit either Fe(3)O(4) (magnetite) or gamma-Fe(2)O(3) (maghemite) phases, as verified by electron microscopy, X-ray and electron diffraction, microprobe Raman spectroscopy, and magnetic analysis. Peak deconvolution of the Raman-active Fe-O bands yields valuable information on the local structure and vacancy content of the various aerogel forms, and facilitates the differentiation of Fe(3)O(4) and gamma-Fe(2)O(3) components, which are difficult to assign using only diffraction methods. These nanocrystalline, magnetic forms retain the inherent characteristics of aerogels, including high surface area (>140 m(2) g(-1)), through-connected porosity concentrated in the mesopore size range (2-50 nm), and nanoscale particle sizes (7-18 nm). On the basis of this synthetic and processing protocol, we produce multifunctional nanostructured materials with effective control of the pore-solid architecture, the nanocrystalline phase, and subsequent magnetic properties.     

硅含量对Al2O3-SiO2气凝胶结构和性能的影响

研究了硅含量对Al2O3-SiO2气凝胶结构和性能的影响.结果表明,随着硅含量的增加,Al2O3-SiO2溶胶的凝胶时间逐渐延长,气凝胶密度逐渐增大.其结构逐渐由多晶勃姆石向无定形SiO2过渡.Al2O3-SiO2气凝胶同时含有Al-O、Si-O以及Al-O-Si结构,600 ℃煅烧后的物相为无定形γ-Al2O3和SiO2,1 200 ℃煅烧后为莫来石相.当硅含量为6.1wt%～13.1wt%时,适量的硅抑制了Al2O3-SiO2气凝胶的相变,其1 000℃的比表面积(339～445 m2·g-1)高于纯Al2O3气凝胶(157 m2·g-1).SEM分析表明,硅元素的加入改变了Al2O3气凝胶的结构形貌,随着硅含量的增大,Al2O3-SiO2气凝胶逐渐由针叶状或长条状向球状颗粒转变.     

Mechanical behaviour of nano composite aerogels

In order to improve the mechanical properties of silica aerogels, we propose the synthesis of nano composite aerogels. Silica particles (20–100 nm) are added in the monomer solution, just before gelling and supercritical drying. The silica particles addition increases the mechanical properties, but also affects the aggregation process, the aerogel structure and the pore sizes. We discuss the different parameters which infer in the mechanical behaviour of silica aerogel such as: brittle behaviour, load bearing fraction of solid (pore volume), internal stresses (shrinkage), size and distribution of flaws, subcritical flaws propagation (chemical susceptibility). With silica particles addition, the mechanical properties rapidly increase, stiffening and strengthening the structure by a factor 4–8. Moreover, the mechanical strength distribution and the Weibull modulus characterizing the statistical nature of flaws size in brittle materials show a more homogeneous strength distribution. The composite structure is made of two imbricate networks, the polymeric silica and the particles silica networks. Ultra Small Angle X-ray Scattering experiments show that besides the fractal network usually built up by the organosiloxane, the silica particles is forming another fractal structure at a higher scale. The fractal structure could be related to the low Weibull parameter characteristic of a large flaws size distribution, pores being the critical flaws.     

Ultra porous nanocellulose aerogels as separation medium for mixtures of oil/water liquids

A novel type of sponge-like material for the separation of mixed oil and water liquids has been prepared by the vapour deposition of hydrophobic silanes on ultra-porous nanocellulose aerogels. To achieve this, a highly porous (>99%) nanocellulose aerogel with high structural flexibility and robustness is first formed by freeze-drying an aqueous dispersion of the nanocellulose. The density, pore size distribution and wetting properties of the aerogel can be tuned by selecting the concentration of the nanocellulose dispersion before freeze-drying. The hydrophobic light- weight aerogels are almost instantly filled with the oil phase when selectively absorbing oil from water, with a capacity to absorb up to 45 times their own weight in oil. The oil can also be drained from the aerogel and the aerogel can then be reused for a second absorption cycle.     

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.     

Sol-Gel assembly of CdSe nanoparticles to form porous aerogel networks

A detailed study of CdSe aerogels prepared by oxidative aggregation of primary nanoparticles (prepared at room temperature and high temperature conditions, >250 degrees C), followed by CO2 supercritical drying, is described. The resultant materials are mesoporous, with an interconnected network of colloidal nanoparticles, and exhibit BET surface areas up to 224 m2/g and BJH average pore diameters in the range of 16-32 nm. Powder X-ray diffraction studies indicate that these materials retain the crystal structure of the primary nanoparticles, with a slight increase in primary particle size upon gelation and aerogel formation. Optical band gap measurements and photoluminescence studies show that the as-prepared aerogels retain the quantum-confined optical properties of the nanoparticle building blocks despite being connected into a 3-D network. The specific optical characteristics of the aerogel can be further modified by surface ligand exchange at the wet-gel stage, without destroying the gel network.     

RF-aerogels catalysed by ammonium carbonate

The application of ammonium carbonate (AC) as catalyst for the preparation of RF-aerogels leads to organic aerogels without metallic impurities in contrast to conventional catalysts like sodium carbonate. To synthesize the AC catalyzed RF aerogels we varied the catalyst and formaldehyde concentration in wide ranges. The nanostructure varies accordingly over an order of magnitude. The particle sizes in the dry aerogel network, determined by scanning electron microscopy, are in the range of 0.15–4 μm. The aerogel densities are in the range of 370–420 kg m⁻³. The specific surface measured by nitrogen adsorption (BET) varies from 0.5 to 13 m² g⁻¹ which equals a specific surface area from 0.7 to 20 μm⁻¹. Thermogravimetry is employed to study the drying process, annealing reactions and decomposition of the aerogel into a carbon aerogel.     

Absorption and desorption of organic liquids in elastic superhydrophobic silica aerogels

The experimental results of the studies on the absorption and desorption of organic liquids in elastic superhydrophobic silica aerogels, are reported. The elastic superhydrophobic aerogels were prepared using methyltrimethoxysilane (MTMS) precursor by a two-step sol-gel process followed by supercritical drying. Monolithic superhydrophobic silica aerogels were used as the absorbents. In all, four alkanes, three aromatic compounds, four alcohols and three oils were used. The absorption property of the aerogel was quantified by the mass and moles of the organic liquid absorbed by unit mass of the aerogel. The superhydrophobic aerogels showed a very high uptake capacity and high rate of uptake. The desorption of solvents and oils was studied by maintaining the as-absorbed aerogel samples at various temperatures and weighing them at regular time intervals until all the absorbed liquid got totally desorbed. This was verified by measuring the weights of the aerogel samples before and after desorption. The transmission electron micrograph observations showed that the aerogel structure was not much affected by the solvent absorption, while the oil absorption led to the shrinkage resulting in a dense structure after the desorption. In all the cases, the aerogels retained hydrophobicity and could be re-used as absorbents.     

Gold modified cadmium sulfide aerogels

Monolithic aerogels composed of cadmium sulfide nanoparticles partially modified with metallic gold (CdS-Au) are reported. The semiconductor–metal nanoparticles are synthesized using an inverse micelle media of Bis-(2-ethylhexyl)sulfosuccinate sodium salt (AOT) in heptane, followed by capping with 4-fluorothiophenol and precipitation with triethylamine. The nanoparticles are then dispersed in acetone and gel formation is achieved using nanoparticle condensation strategy. The resultant CdS-Au aerogel materials are mesoporous, with an interconnected network of semiconductor–metal nanoparticles. A detailed microstructure analysis of the semiconductor–metal aerogels via transmission electron microscopy indicates that the final gold concentration significantly impacts the semiconductor–metal aerogel morphology and porosity.     

Biopolymer Aerogels and Foams: Chemistry,Properties, and Applications

Biopolymer aerogels were among the first aerogels produced, but only in the last decade has research on biopolymer and biopolymer–composite aerogels become popular, motivated by sustainability arguments, their unique and tunable properties, and ease of functionalization. Biopolymer aerogels and open‐cell foams have great potential for classical aerogel applications such as thermal insulation, as well as emerging applications in filtration, oil–water separation, CO₂ capture, catalysis, and medicine. The biopolymer aerogel field today is driven forward by empirical materials discovery at the laboratory scale, but requires a firmer theoretical basis and pilot studies to close the gap to market. This Review includes a database with over 3800 biopolymer aerogel properties, evaluates the state of the biopolymer aerogel field, and critically discusses the scientific, technological, and commercial barriers to the commercialization of these exciting materials.