Superhydrophobic and superoleophobic nanocellulose aerogel membranes as bioinspired cargo carriers on water and oil

We demonstrate that superhydrophobic and superoleophobic nanocellulose aerogels, consisting of fibrillar networks and aggregates with structures at different length scales, support considerable load on a water surface and also on oils as inspired by floatation of insects on water due to their superhydrophobic legs. The aerogel is capable of supporting a weight nearly 3 orders of magnitude larger than the weight of the aerogel itself. The load support is achieved by surface tension acting at different length scales: at the macroscopic scale along the perimeter of the carrier, and at the microscopic scale along the cellulose nanofibers by preventing soaking of the aerogel thus ensuring buoyancy. Furthermore, we demonstrate high-adhesive pinning of water and oil droplets, gas permeability, light reflection at the plastron in water and oil, and viscous drag reduction of the fluorinated aerogel in contact with oil. We foresee applications including buoyant, gas permeable, dirt-repellent coatings for miniature sensors and other devices floating on generic liquid surfaces.     

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.     

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.     

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.     

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.     

Shape-Memory and Anisotropic Carbon Aerogel from Biomass and Graphene Oxide

Biomass, as the most abundant and sustainable resource on the earth, has been regarded as an ideal carbon source to prepare various carbon materials. However, manufacturing shape-memory carbon aerogels with excellent compressibility and elasticity from biomass remains an open challenge. Herein, a cellulose-derived carbon aerogel with an anisotropic architecture is fabricated with the assistance of graphene oxide (GO) through a directional freeze-drying process and carbonization. The carbon aerogel displays excellent shape-memory performances, with high stress and height retentions of 93.6% and 95.5% after 1000 compression cycles, respectively. Moreover, the carbon aerogel can identify large ranges of compression strain (10–80%), and demonstrates excellent current stability during cyclic compression. The carbon aerogel can precisely capture a variety of biological signals in the human body, and thus can be used in wearable electronic devices.     

Thermally stable and flame-retardant poly(vinyl alcohol)/montmorillonite aerogel via a facile heat treatment

The PVA/MMT aerogels prepared by a simple freeze-drying and heat treatment process exhibited a significant improvement of thermal stability and flame retardant property.     

Aerogels with 3D Ordered Nanofiber Skeletons of Liquid‐Crystalline Nanocellulose Derivatives as Tough and Transparent Insulators

Aerogels of high porosity and with a large internal surface area exhibit outstanding performances as thermal, acoustic, or electrical insulators. However, most aerogels are mechanically brittle and optically opaque, and the structural and physical properties of aerogels strongly depend on their densities. The unfavorable characteristics of aerogels are intrinsic to their skeletal structures consisting of randomly interconnected spherical nanoparticles. A structurally new type of aerogel with a three‐dimensionally ordered nanofiber skeleton of liquid‐crystalline nanocellulose (LC‐NCell) is now reported. This LC‐NCell material is composed of mechanically strong, surface‐carboxylated cellulose nanofibers dispersed in a nematic LC order. The LC‐NCell aerogels are transparent and combine mechanical toughness and good insulation properties. These properties of the LC‐NCell aerogels could also be readily controlled.     

Partial transesterification of sunflower oil with ethanol by a silica fiber reinforced aerogel encapsulated lipase

A commercial lyophilized lipase of Burkholderia cepacia, from Amano, was encapsulated in silica aerogels reinforced with silica quartz fiber felt. This biocatalyst was applied in the direct transesterification of sunflower seed oil with ethanol, without any other solvent. When the molar ratio of ethanol to oil was two or three, the oil transformation kinetics was found to be very slow after the formation of 1 mole of fatty ethyl ester per mole of initial triglyceride. For a molar proportion of ethanol to oil ≈1, the recycling activity also decreased gradually in successive tests to reach an activity ≈7% of the initial activity, during the 5th test. Textural and structural analysis of the aerogels before and after catalytic tests showed that this deterioration was associated with a modification of the aerogel, by preferential adsorption of glycerol or possibly other transesterification products such as diglycerides. Besides, it is proposed that one of the cause for the aerogel loss of activity at an initial molar ratio of ethanol:oil of 3:1 was due to a progressive inhibition of the enzyme by excess adsorbed ethanol. The aerogel samples were also compared to a commercial product of lipase immobilized on polymer beads, from Fluka. The silica aerogels somewhat improved, to a limited extent, the activity during recycling.     

Adsorption of toxic organic compounds from water with hydrophobic silica aerogels

Silica monolith aerogels with different degrees of hydrophobicity were prepared by incorporating methyltrimethoxysilane (MTMS) or trimethylethoxysilane (TMES) in standard sol-gel synthesis followed by supercritical drying of gels with carbon dioxide (CO(2)) at 40 degrees C and 100 bar. The hydrophobicity of the aerogels was tested by measuring the contact angle (theta). The aerogels were also characterised by FTIR, DSC, and porosity measurements. Adsorption capacity measurements show that such modified hydrophobic silica aerogels are excellent adsorbents for different toxic organic compounds from water. In comparison to granulated active carbon (GAC) they exhibit capacities which are from 15 to 400 times higher for all tested compounds. Adsorption properties of hydrophobic silica aerogel remain stable even after 20 adsorption/desorption cycles.     

3D-Printed Nanocellulose-Based Cushioning–Antibacterial Dual-Function Food Packaging Aerogel

Cushioning and antibacterial packaging are the requirements of the storage and transportation of fruits and vegetables, which are essential for reducing the irreversible quality loss during the process. Herein, the composite of carboxymethyl nanocellulose, glycerin, and acrylamide derivatives acted as the shell and chitosan/AgNPs were immobilized in the core by using coaxial 3D-printing technology. Thus, the 3D-printed cushioning–antibacterial dual-function packaging aerogel with a shell–core structure (CNGA/C–AgNPs) was obtained. The CNGA/C–AgNPs packaging aerogel had good cushioning and resilience performance, and the average compression resilience rate was more than 90%. Although AgNPs was slowly released, CNGA/C–AgNPs packaging aerogel had an obvious antibacterial effect on E. coli and S. aureus. Moreover, the CNGA/C–AgNPs packaging aerogel was biodegradable. Due to the customization capabilities of 3D-printing technology, the prepared packaging aerogel can be adapted to more application scenarios by accurately designing and regulating the microstructure of aerogels, which provides a new idea for the development of food intelligent packaging.     

Silica–titania aerogel monoliths with large pore volume and surface area by ambient pressure drying

Ambient pressure drying has been carried out for the synthesis of silica–titania aerogel monoliths. The prepared aerogels show densities in the range 0.34–0.38 g/cm³. The surface area and pore volume of these mixed oxide aerogels are comparable to those of the supercritically dried ones. The surface area for 5wt% titania aerogel has been found to be as high as 685 m²/g with a pore volume of 2.34 cm³/g and the 10wt% titania aerogel has a surface area of 620 m²/g with a pore volume of 2.36 cm³/g. Some gels were also made hydrophobic by a surface treatment with methyltrimethoxysilane and trimethylchlorosilane. The surface modified aerogels possess high surface areas in the range of 540–640 m²/g, and are thermally stable in terms of retaining hydrophobicity up to a temperature of 520 °C. The pore size distribution of the aerogels clearly indicates the preservation of the aerogel structure. High Resolution Transmission Electron microscopy has been employed to characterise the aerogels and Fourier Transform infrared spectroscopy to study the effect of titania addition to silica and the surface modification. X-ray diffraction patterns were recorded to verify the molecular homogeneity of the aerogel.     

Soy protein–nanocellulose composite aerogels

Organic aerogels based on two important and widely abundant renewable resources, soy proteins (SP) and nanofibrillar cellulose (NFC) are developed from precursor aqueous dispersions and a facile method conducive of channel- and defect-free systems after cooling and freeze-drying cycles that yielded apparent densities on the order of 0.1 g/cm³. NFC loading drives the internal morphology of the composite aerogels to transition from network- to fibrillar-like, with high density of interconnected cells. Composite aerogels with SP loadings as high as ca. 70 % display a compression modulus of 4.4 MPa very close to that obtained from reference, pure NFC aerogels. Thus, the high compression modulus of the composite system is not compromised as long as a relatively low amount of reinforcing NFC is present. The composite materials gain moisture (up to 5 %) in equilibrium with 50 % RH air, independent of SP content. Furthermore, their physical integrity is unchanged upon immersion in polar and non-polar solvents. Fast liquid sorption rates are observed in the case of composite aerogels in contact with hexane. In contrast, water sorption is modulated by the chemical composition of the aerogel, with an important contribution from swelling. The potential functionalities of the newly developed SP–NFC composite green materials can benefit from the reduced material cost and the chemical features brought about the amino acids present in SPs.     

Preparation and characterization of silica aerogels from diatomite via ambient pressure drying

The silica aerogels were successfully fabricated under ambient pressure from diatomite. The influence of different dilution ratios of diatomite filtrate on physical properties of aerogels were studied. The microstructure, surface functional groups, thermal stability, morphology and mechanical properties of silica aerogels based on diatomite were investigated by BET adsorption, FT-IR, DTA-TG, FESEM, TEM, and nanoindentation methods. The results indicate that the filtrate diluted with distilled water in a proportion of 1: 2 could give silica aerogels in the largest size with highest transparency. The obtained aerogels with density of 0.122–0.203 g/m³ and specific surface area of 655.5–790.7 m²/g are crack free amorphous solids and exhibited a sponge-like structure. Moreover, the peak pore size resided at 9 nm. The initial aerogels were hydrophobic, when being heat-treated around 400°C, the aerogels were transformed into hydrophilic ones. The obtained aerogel has good mechanical properties.     

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。     

Application of hydrophobic silica based aerogels and xerogels for removal of toxic organic compounds from aqueous solutions

This work is devoted to the application of hydrophobic silica based aerogels and xerogels for the removal of three toxic organic compounds from aqueous solutions. These materials were tested and characterized regarding their morphology, particle size distribution, surface area and porous structure. The equilibrium tests were carried out at different adsorbate concentrations and the experimental data were correlated by means of Langmuir and Freundlich isotherms. The equilibrium data were well described by Langmuir and Freundlich in most cases. The maximum adsorption capacity by Langmuir model was observed for the adsorption of benzene onto aerogel (192.31 mg/g), though the most promising results were obtained for toluene adsorption due to the greater adsorption energy involved. Comparing these results with other reported results, the hydrophobic silica based aerogels/xerogels were found to exhibit a remarkable performance for the removal of benzene and toluene. In addition, the regeneration of previously saturated aerogel/toluene was also investigated by using an ozonation process. The adsorption/regeneration tests with ozone oxidation showed that the aerogel might be regenerated, nevertheless the materials lost their hydrophobicity and thus different methods should be evaluated in forthcoming investigations.     

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.     

Loading of Bacterial Cellulose Aerogels with Bioactive Compounds by Antisolvent Precipitation with Supercritical Carbon Dioxide

Bacterial cellulose aerogels overcome the drawback of shrinking during preparation by drying with supercritical CO₂. Thus, the pore network of these gels is fully accessible. These materials can be fully rewetted to 100% of its initial water content, without collapsing of the structure due to surface tension of the rewetting solvent. This rehydration property and the high pore volume of these material rendered bacterial cellulose aerogels very interesting as controlled release matrices. Supercritical CO₂ drying, the method of choice for aerogel preparation, can simultaneously be used to precipitate solutes within the cellulose matrix and thus to load bacterial cellulose aerogels with active substances. This process, frequently termed supercritical antisolvent precipitation, is able to perform production of the actual aerogel and its loading in one single preparation step. In this work, the loading of a bacterial cellulose aerogel matrix with two model substances, namely dexpanthenol and L-ascorbic acid, and the release behavior from the matrix were studied. A mathematical release model was applied to model the interactions between the solutes and the cellulose matrix. The bacterial cellulose aerogels were easily equipped with the reagents by supercritical antisolvent precipitation. Loading isotherms as well as release kinetics indicated no specific interaction between matrix and loaded substances. Hence, loading and release can be controlled and predicted just by varying the thickness of the gel and the solute concentration in the loading bath.     

Preparation and thermal properties of chemically prepared nanoporous silica aerogels

This work focuses on the dependence preparation conditions—structure—physical properties of hydrophobic silica aerogels, all of them prepared under subcritical drying conditions (70 °C and 0.4 atm.), thus aiming at potential application as case insulation filling in heat pumps. The so prepared, millimeter scaled nano-porous hydrophobic silica aerogel granules were analyzed with standard electron microscope and atomic force microscopy, IR spectroscopy, UV/Vis spectroscopy, differential scanning calorimetry and thermal conductivity measurements. The physical properties of the aerogels were compared with commercial aerogel granules. A method for contact angle measurement of micro-droplets situated on the silica granules was proposed to quantify the level of their hydrophobicity.     

Hydrophobic silica aerogels prepared via rapid supercritical extraction

Hydrophobic silica aerogels have been prepared using the rapid supercritical extraction (RSCE) technique. The RSCE technique is a one-step methanol supercritical extraction method for producing aerogel monoliths in 3 to 8 h. Standard aerogels were prepared from a tetramethoxysilane (TMOS) recipe with a molar ratio of TMOS:MeOH:H₂O:NH₄OH of 1.0:12.0:4.0:7.4 × 10⁻³. Hydrophobic aerogels were prepared using the same recipe except the TMOS was replaced with a mixture of TMOS and one of the following organosilane co-precursors: methytrimethoxysilane (MTMS), ethyltrimethoxysilane (ETMS), or propyltrimeth-oxysilane (PTMS). Results show that, by increasing the amount of catalyst and increasing gelation time, monolithic aerogels can be prepared out of volume mixtures including up to 75% MTMS, 50% ETMS or 50% PTMS in 7.5–15 h. As the amount of co-precursor is increased the aerogels become more hydrophobic (sessile tests with water droplets yield contact angles up to 155°) and less transparent (transmission through a 12.2-mm thick sample decreases from 83 to 50% at 800 nm). The skeletal and bulk density decrease and the surface area increases (550–760 m²/g) when TMOS is substituted with increasing amounts of MTMS. The amount of co-precursor does not affect the thermal conductivity. SEM imaging shows significant differences in the nanostructure for the most hydrophobic surfaces.