Aerogel Membranes Research Articles

Robustly Flexible, Highly Transparent, and Polymerization-Regulated Polyimide Aerogel Membranes as Efficient Thermal Insulators for Solar Collection.

Efficient thermal insulators that can maintain their efficacy at extreme temperatures are in pressing demand, particularly in fields such as energy saving, aerospace, and sophisticated equipment. Herein, a novel and facile polymerization-regulated optimal strategy is adapted to realize the comprehensive performance of polyimide (PI) aerogel membranes with mechanical robustness, high flexibility, hydrophobicity, light transmittance, and efficient thermal insulation. Benefiting from the hydrolysis of monomers and chemical imidization reaction process verified by a thermo-chemo-mechanically coupled theoretical model, the viscosity of precursors, shrinkage rate, and microstructure of aerogels are precisely controlled, leading to a low thermal conductivity range of 0.023-0.044 W/(m·K). The fabricated PI aerogel membranes, which undergo a remarkable transformation from their initial brittle and opaque nature to a state of high flexibility and transparency, exhibit a 3.0 times increase in tensile strength (4.6 MPa) and a 8.4 times improvement in elongation at break (20.6%) over previous studies while demonstrating an exceptional light transmittance of 92.5% across a wide spectral range from 500 to 2500 nm. Additionally, the PI aerogel membranes possess superior mechanical properties and a wide temperature resistance range extending from -196 to 300 °C. These flexible PI aerogel membranes can be effectively adjusted to meet the practical application of a circular ring solar thermal collector, which displayed a high solar heat collection temperature of 135 °C at a thickness of 0.5 mm. The coordination between the thermophysical properties and mechanical properties of the PI aerogel membranes in this work holds great promise for application requirements of thermal insulators in optical elements under harsh environments.

Liquid-infused aerogel membranes with reverse functions enable on-demand emulsification and demulsification

Liquid-infused aerogel membranes with reverse functions enable on-demand emulsification and demulsification

Flexible and high-strength MXene/polyimide nanofiber aerogel membranes achieving infrared stealth through combined thermal control and low emissivity

The development of high-performance infrared stealth materials has been a long-standing goal for scientists. Despite their excellent performance, these materials are challenging to fabricate. In this work, a simple water immerse-stacking assembly process is employed to transform two-dimensional nanofiber membranes into three-dimensional aerogel membranes. Directional freezing from different directions induced varied orientations in the polyimide nanofibers (PINF), leading not only to unique anisotropic microstructures and thermal conductivities but also to synergistic enhancements in thermal insulation and mechanical properties. By vacuum-assisted filtration, MXene is embedded into the PINF membrane, resulting in a low emissivity of 0.283 and strong interlayer bonding of the MXene/PINF aerogel membrane without affecting the high and low-temperature resistance, the tensile strength, and the flexibility. Inspired by the art of origami, two types of MXene/PINF aerogel membrane bags are developed. When using one of the bags to cover an object at 130.2 °C, the thermal radiation temperature decreases to 28.9 °C. This study provides a promising approach for designing flexible, high-strength, and efficient infrared stealth composite materials, paving the way for further research and applications.

Bio-Inspired Underwater Superoleophobic Aramid Nanofiber-Based Aerogel Membranes for Highly Efficient Removal of Emulsified Oils and Organic Dyes.

Effective elimination of insoluble emulsified oils and soluble organic dyes has received extensively attention in wastewater treatment. In this work, a chitosan and polydopamine @ aramid nanofibers (CS&PDA@ANFs) aerogel membrane was fabricated through an integration methodology consisting of phase inversion and successive deposition of PDA and CS. The as-prepared aerogel membrane possessed a satisfactory three-dimensional interpenetrating network architecture with high porosity and desirable mechanical property. Furthermore, due to the synergistic effect of hydrophilic CS and PDA, the resultant membrane exhibited good superhydrophilicity and underwater superoleophobicity associated with favorable oil resistance/antioil fouling properties. The combination of the interconnected porous structures and super wettability endowed the aerogel membranes with desirable oil-in-water emulsion separation performance. Particularly, an extremely high permeation flux (3729 L/m2/h) and a rejection rate (99.3%) were achieved for the CS&PDA@ANFs membrane. Moreover, diverse dyes could be also adsorbed by the resultant membrane, and the equilibrium adsorption capacity of cationic dye malachite green could reach 36 mg/g, with a high rejection rate over 97%. This study indicated that the CS&PDA@ANFs aerogel membrane held great promise for practical applications in complex wastewater remediation.

Design of membrane-based microfluidic chip device based on bionic leaf and adsorption detection of tetracycline antibiotics by specific gel membrane

In this study, we developed copper alginate-carbon nanotube/copper sulfide-graphene oxide gel membranes based on the design inspired by the surface structure of leaves and plant transpiration in nature and through the modulation of high-density polymer networks. This light-driven water evaporation-specific adsorption gel membrane is capable of using solar energy to drive water evaporation from contaminated surface water to access tetracycline antibiotics for detection. Combined with the designed biomimetic adsorption detection chip, in situ monitoring of tetracycline antibiotics in water bodies was achieved. Compared with the traditional mass spectrometry detection method, it shows more outstanding performance in terms of time, environmental protection and technology. The microscale adsorption mechanism was further explored on the molecular scale by density functional theory (DFT). The results showed that tetracycline antibiotics were adsorbed on the aerogel membrane mainly through π-πEDA interactions in sandwich (S) configuration and parallel displacement (PD) configuration, which ensured high adsorption efficiency. Under the optimized conditions, the tetracycline concentration detected by the sensor showed a good linear relationship with the cyclic voltammetry curve, and the lowest detection limit was 1.59*10−4 μM. This adsorption detection strategy can reduce the influence of organic matter, inorganic matter, and other classes of antibiotics on the detection of tetracycline antibiotics, and provide a new idea for the high-efficiency photo-thermal actuation and in-situ testing of tetracycline antibiotics.

Double-drying 3D lamellar-structured aerogel membrane for efficient oil-water separation and long-lasting antibacterial activity

Conventional oil-water separation membranes are difficult to establish a trade-off between membrane flux and separation efficiency, and often result in serious secondary contamination due to their fouling issue and non-degradability. Herein, a double drying strategy was introduced through a combination of oven-drying and freeze-drying to create a super-wettable and eco-friendly oil-water separating aerogel membrane (TMAdf). Due to the regular nacre-like structures developed in the drying process and the pores formed by freeze-drying, TMAdf aerogel membrane finally develops regularly arranged porous structures. In addition, the aerogel membrane possesses excellent underwater superoleophobicity with a contact angle above 168° and antifouling properties. TMAdf aerogel membrane can effectively separate different kinds of oil-water mixtures and highly emulsified oil-water dispersions under gravity alone, achieving exceptionally high flux (3693 L·m−2·h−1) and efficiency (99 %), while being recyclable. The aerogel membrane also displays stability and universality, making it effective in removing oil droplets from water in corrosive environments such as acids, salts and alkalis. Furthermore, TMAdf aerogel membrane shows long-lasting antibacterial properties (photothermal sterilization up to 6 times) and biodegradability (completely degraded after 50 days in soil). This study presents new ideas and insights for the fabrication of multifunctional membranes for oil-water separation.

Eco-friendly biomass aerogels from moxibustion waste for sustainable remediation of organic contaminants

Powder adsorbents present limited recyclability when used for wastewater treatment. Bulk materials prepared via eco-friendly approaches typically exhibit excellent reproducibility over powders in terms of removing pollutants from aquatic environments. Here, biomass-based aerogels were synthesized via ball milling a mixture of modified moxa ash (a type of moxibustion waste), carbon nanotubes and ammonia, combined with agarose as biomolecule. The obtained aerogels display low density, high porosity, remarkable mechanical properties, and exceptional repeatability and stability for removing organic pollutants. By employing a two-dimensional (2D) aerogel membrane, pollutants such as 10 mg/L mitoxantrone (MTX), 5 mg/L methylene blue, 5 mg/L malachite green, or 5 mg/L rhodamine B could be dynamically adsorbed and swiftly filtered out, achieving nearly 100 % of the removal rate. For three-dimensional (3D) aerogels, efficient removals of MTX (98.4 % at 135 min) and cationic dyes under various conditions were observed, in which the adsorption capacity reached 28.23 mg/g for low concentration of MTX at 120 min. After four cycles, the aerogel still retained 93 % of its original capacity and the removal rate was still 92.4 %. The adsorption process obeys second-order kinetics and adheres to the Freundlich and Temkin isotherm models. Furthermore, the primary mechanism by which the aerogels adsorb MTX includes pore filling, electrostatic interactions, π-π conjugation and hydrogen bonding. The adsorption mechanism was better explained by the results of density functional theory. Biomass-based 2D/3D aerogels are promising, low-cost, eco-friendly and highly efficient absorbents for mitigating wastewater contamination.

Robust-flexible and highly-thermostable polyimide-silica aerogels with adjustable fiber skeleton structure for efficient aerospace thermal protection

The rapid growth of the aerospace industry presents significant challenges in developing lightweight and flexible thermal protective materials for spacecraft and related equipment. One longstanding challenge has been the preparation of high-thermostable and highly flexible aerogels, which limits their practical application in flexible thermal protection. In this work, through a rational 'chain-sphere' dual-combination structure design, polyimide-silica aerogels with integrated properties of the adjustable aerogel-fiber skeleton structure, robust flexibility and high thermostable have been prepared. By incorporating 2,2-dimethylbenzidine (DMBZ), we achieve a more solid aerogel network. The aerogel membrane retains its original shape without creases or cracks even after undergoing 500 folding and unfolding tests. Additionally, the silicon nanoparticles surrounding the aerogel exhibit superior performance at high temperatures. The unique structure and components of the composite enable it to possess lightweight (0.075–0.11 g/cm−3), low thermal shrinkage (300℃∼6 %), excellent thermostability (95 % weight retention at 474℃∼557℃), and promising thermal insulating performance below 600℃. The integrated performances of the aerogel make it suitable for high-temperature thermal protection applications that require both efficient thermal insulation and robust flexibility.

Kevlar Aerogel‐Confined Functional Liquid‐Based Composite Membrane Enables Dynamic Uranium Capture

AbstractSolid–liquid composite materials that confine a functional liquid within a porous solid have appeared in a wealth of emerging applications. However, creating dynamic liquid interfaces for efficient ion capture while stably retaining functional liquid in porous confinements is challenging. Here, an aerogel‐confined liquid‐based composite membrane (ALCM) for dynamic and highly efficient uranium capture is reported. As a proof of concept, Kevlar aerogel membrane is selected as the nanoporous solid, and calix[6]arene/tributyl phosphate (C6/TBP) is used as the guest liquid. The obtained ALCMs possess high stability, optimum adhesion between solid‐liquid interface, and high selectivity for uranyl ions (250–6510 times over other competing ions). Different dynamic interface regulating approaches are explored for ALCMs, and uranium extraction efficiency under alternating pressures can be up to 258.48 mg g−1 h−1, outperforming many reported uranium capture materials. This strategy can be applicable to develop a rich family of solid‐liquid composite materials and may spearhead a new paradigm for uranium capture from sustainable seawater resources.

Application of MOF-based membrane in oil-water separation

In addition to being a serious threat to human health and the natural environment, the rising volume of oily wastewater and oil spills also causes resource depletion. Thus, there is a lot of interest in effective oil-water (O/W) separation. Scientists have looked at and suggested a variety of creative separation techniques in an attempt to address this issue. Unfortunately, the majority of these techniques have technical issues with low separation efficiency and significant energy usage. It is crucial to develop an effective oil-water separation membrane in order to address this issue. Because of their large surface area, low density, high porosity, controllable wettability, and variable pore size, have a lot of potential in this sector. This paper first categorizes several different MOF-based membranes and describe in detail their different synthesis methods, including solvent thermal method, ultrasonic method, microwave method, etc. Then, the physicochemical properties of MOF-based films are summarized in detail. The mechanism by which MOF-based films can separate oil-water mixtures is also explained. Finally, the modification of stainless steel mesh, sponge, aerogel and filtration membranes by MOF-based films, respectively, is emphasized and their applications in O/W separation are discussed.

High-aligned oppositely-charged nanocellulose/MXene aerogel membranes through synergy of directional freeze-casting and structural densification for osmotic-energy harvesting

Optimization of ion-transport paths can considerably improve ion-transport capabilities in charged nanochannels. Thus, the assembly of high-charge-density one- and two-dimensional nanomaterials into aligned nanochannels is necessary for high-performance osmotic-energy harvesting. Herein, we prepared cellulose/MXene aerogel membranes with opposite charges and aligned nanochannels via chemical modification on algal cellulose nanofibers and MXene nanosheets, unidirectional freeze casting, and structural densification to considerably enhance the ionic conductivity in low-concentration solutions (maximum conductivity of 2.88 × 10−3 S cm−1). In particular, the aligned membrane had an output power density of 2.97 and 4.89 times higher than membranes used for suction filtration and isotropic nanochannels, respectively, demonstrating the necessity for nanostructure control. In addition, due to the photothermal effect of MXene, the positively–negatively (P–N) charged unit produced a maximum output power density of 8.87 W m−2 under a concentration gradient of artificial seawater and river water and simulated sunlight. Moreover, the unit maintained 90.4% of its original output capacity after 168 h of operation. As a proof of concept, we created nine series of P–N units and successfully powered an electronic calculator with an output voltage of 1.85 V. This study reveals improvements in developing renewable materials with an aligned nanostructure for high-performance osmotic-energy conversion.

Cuttlefish ink nanoparticles-integrated aerogel membranes for efficient solar steam generation

Cuttlefish inks offer nano-solar-absorbers for obtaining freshwater through interfacial evaporation.

3D aerogel membrane-based evaporator with sandwich structure for superior solar-driven evaporation

Seawater desalination with solar-driven interfacial evaporators has emerged as a promising solution to alleviate global water scarcity. However, conventional two-dimensional (2D) planar evaporators have high reflectivity, which poses a challenge in achieving efficient light absorption. Herein, a sandwich-structured solar-driven interfacial evaporator (SSIE) assembled with three-dimensional (3D) cellulose aerogel membranes (modified with TiN nanoparticles) and an air-laid paper was proposed, which is significantly different from the previously reported 2D membrane-based evaporators. Cellulose aerogel membranes have excellent integrated properties, including extremely high flexibility, allowing for multiple folds, and a 3D porous structure that enables multiple light absorptions. Benefiting from special structural design, SSIE achieves an outstanding evaporation rate of 2.20 kg m−2 h−1 and an energy efficiency of 83.30%. Moreover, SSIE maintains a stable evaporation rate throughout a 10 h saltwater evaporation process. It also demonstrates excellent performance in seawater and simulated wastewater purification. Furthermore, SSIE exhibits a significant purification effect for dye wastewater, such as Rhodamine B (RhB). This study provides valuable insights into rational structural design for solar evaporators, as well as holding tremendous potential for carrying out seawater desalination in limited spaces.

Moisture resistant polyimide aerogel membranes with low dielectric constant and super thermal insulation for electronic device under harsh environment

Membranes with low dielectric constant and high moisture resistance are the key material for miniaturized and integrated communication equipment as an interlayer dielectric layer. Here, a series of cross-linked PI aerogel membranes were prepared by co-polymerization and scraping coating technology. The introduction of the fluorinated blocks and benzimidazole ring structures can consequently garner novel PI aerogel membranes with fascinating dielectric properties and outstanding moisture resistance. The dielectric constants of the sample membranes are as low as 1.33 at 1 KHz and 1.32 at 1 MHz with dielectric loss as low as 0.0079 at 1 KHz and 0.0035 at 1 MHz. The water contact angle can reach 107.35° with a surface roughness value of 30.428 nm. Moreover, the PI aerogel membranes have high specific surface area and excellent thermal and mechanical properties. The thermal conductivity as low as 35.4 mW m−1 K−1 at room temperature indicates excellent thermal insulation performance. PIAM-2 is suitable as an interlayer dielectric layer for electronic components under harsh environment. In addition, the influence of surface roughness on surface wettability was also elaborated on which can provide a feasible method for the preparation of low dielectric materials with moisture resistance.

A Hierarchically Nanofibrous Self-Cleaning Textile for Efficient Personal Thermal Management in Severe Hot and Cold Environments.

Climate change has recently caused more and more severe temperatures, inducing a growing demand for personal thermal management at outdoors. However, designing textiles that can achieve personal thermoregulation without energy consumption in severely hot and cold environments remains a huge challenge. Herein, a hierarchically nanofibrous (HNF) textile with improved thermal insulation and radiative thermal management functions is fabricated for efficient personal thermal management in severe temperatures. The textile consists of a radiative cooling layer, an intermediate thermal insulation layer, and a radiative heating layer, wherein the porous lignocellulose aerogel membrane (LCAM) as intermediate layer has low thermal conductivity (0.0366 W·m-1·K-1), ensuring less heat loss in cold weather and blocking external heat in hot weather. The introduction of polydimethylsiloxane (PDMS) increases the thermal emissivity (90.4%) of the radiative cooling layer in the atmospheric window and also endows it with a perfect self-cleaning performance. Solar absorptivity (80.1%) of the radiative heating layer is dramatically increased by adding only 0.05 wt% of carbon nanotubes (CNTs) into polyacrylonitrile. An outdoor test demonstrates that the HNF textile can achieve a temperature drop of 7.2 °C compared with white cotton in a hot environment and can be as high as 12.2 °C warmer than black cotton in a cold environment. In addition, the HNF textile possesses excellent moisture permeability, breathability, and directional perspiration performances, making it promising for personal thermal management in severely hot and cold environments.

Integrated asymmetric cellulose aerogel membrane with triple thermal insulation and unidirectional liquid penetration for personal thermal management

With the rapid development of personal thermal management, there is an urgent need for an advanced material that can effectively integrate various thermal functions to keep body warm and cope with the cold outdoor environment. Herein, a multifunctional cellulose based asymmetric modification aerogel membrane (ACAM) encompassing thermal insulation, thermal radiation reflection, solar adsorption, and directional perspiration has been fabricated via bottom-up assembling biomass sisal fibers and pulp fibers into cellulose aerogel membrane, followed by spin-coating ionic liquid modified graphene (IGNs) and silver nanowires (AgNWs) on both sides of the cellulose aerogel membrane, respectively. The results showed that the temperature on the IGNs side is 14.2 °C higher than that of the cotton cloth after 30 s of sunlight exposure. Compared with pure cellulose aerogel membrane, the AgNWs side of ACAM has lower infrared emissivity and higher infrared reflectivity, and the temperature is reduced by 3.2 °C in indoor environment. In addition, the ACAM has asymmetric wettability, which facilitates the transfer of sweat from the hydrophobic side to the hydrophilic side and perspiration penetration was achieved in 10.6 s to obtain the comfort of wearing. The ACAM also exhibits excellent breathability, easy preparation and controllable functional structures. This work may provide a new idea for heat management and dynamic moisture to ensure maximum comfort in very harsh environments.

Preparation of multifunctional Ag@PAN/PBA nanofibrous aerogel membranes for efficient PM 0.3 capture and effective antibacterial activity

AbstractNanofibrous aerogels (NFAs) have great application potential in air filtration due to their unique hierarchical porous structure and high porosity. However, the development of air filter with high air filtration efficiency, as well as good antibacterial activity, remains a major challenge. In an effort to overcome this challenge, here we report a facile methodology for the fabrication of robust and flexible nanofibrous aerogel membranes (NFAMs) with a three‐dimensional (3D) hierarchical porous structure. Moreover, the microstructures and filtration performance of the obtained NFAMs could be easily tuned by adjusting the nanofiber concentration in the aerogel. The resultant Ag@PAN/PBA NFAMs had high filtration efficiency (99.82%) towards PM0.3, low pressure drop (134 Pa) and desirable quality factor (0.0472 Pa−1) under an airflow velocity of 32 L/min. Furthermore, the NFAMs also exhibited excellent antibacterial activities against Escherichia coli (99.46%) and Staphylococcus aureus (99.72%). Together, the results presented here suggest that Ag@PAN/PBA NFAMs have great potential in public health protection applications.

Nanostructured carboxylated-wood aerogel membrane for high-efficiency removal of Cu (II) ions from wastewater

Heavy-metal pollution is a significant environmental issue that has raised global concern due to its harmful impact on humans and the natural ecosystem. Heavy metal pollution poses several challenges in terms of remediation, including low adsorption capacity and efficiency, scale-up issues and non-degradability. Here, we developed an eco-friendly tunable dual-wavelength absorption mesoporous wood aerogel (TDWA) for removal of Cu2+ ions from wastewater based on wood nanotechnology and carboxylated functionalization treatment. Nanostructured pores generated from the cell walls with carboxyl groups due to the removal of most lignin/hemicellulose and 2,2,6,6-tetramethylpiperidine oxidation. Mechanical compression was parallelly applied to the transverse direction of TDWA resulted in removing micron-scale cell cavity and intercellular, which significantly improved the dynamic adsorption performance with an excellent Cu2+ adsorption capacity of 115 mg g−1. This value is superior to most wood-based adsorption membrane as wastewater mainly flowed through the continuous microfibril network in the cell wall. The double-layer mesoporous TDWA membrane (5 mm) possessed a favorable removal efficiency (99.83 %) even after 5-cyclic adsorption (92.34 %). The invented nanostructured TDWA membrane in the current study has promising potential to substitute the present plastic-based membrane in the realistic Cu2+ adsorption because of the facile technology, renewability and high removal efficient, as well as the complete biodegradability.

Designing Highly Photoactive Hybrid Aerogels for In-Flow Photocatalytic Contaminant Removal Using Silica-Coated Bacterial Nanocellulose Supports.

This study explores the use of silica-coated bacterial nanocellulose (BC) scaffolds with bulk macroscopic yet nanometric internal pores/structures as functional supports for high surface area titania aerogel photocatalysts to design flexible, self-standing, porous, and recyclable BC@SiO2-TiO2 hybrid organic-inorganic aerogel membranes for effective in-flow photo-assisted removal of organic pollutants. The hybrid aerogels were prepared by sequential sol-gel deposition of the SiO2 layer over BC, followed by coating of the resulting BC@SiO2 membranes with a porous titania aerogel overlayer of high surface area using epoxide-driven gelation, hydrothermal crystallization, and subsequent supercritical drying. The silica interlayer between the nanocellulose biopolymer scaffold and the titania photocatalyst was found to greatly influence the structure and composition, particularly the TiO2 loading, of the prepared hybrid aerogel membranes, allowing the development of photochemically stable aerogel materials with increased surface area/pore volume and higher photocatalytic activity. The optimized BC@SiO2-TiO2 hybrid aerogel showed up to 12 times faster in-flow photocatalytic removal of methylene blue dye from aqueous solution in comparison with bare BC/TiO2 aerogels and outperformed most of the supported-titania materials reported earlier. Moreover, the developed hybrid aerogels were successfully employed to remove sertraline drug, a model emergent contaminant, from aqueous solution, thus further demonstrating their potential for water purification.

Hemocompatibility of cellulose phosphate aerogel membranes with potential use in bone tissue engineering.

Cellulose is an appealing material for tissue engineering. In an attempt to overcome some obstacles with cellulose II cell scaffolding materials related to insufficient biomineralization, lack of micron-size porosity, and deficiency in surface charge, respective solutions have been proposed. These included covalent phosphorylation of different cellulose materials targeting relatively low degrees of substitution (DS 0.18-0.23) and processing these cellulose derivatives into scaffolding materials by a dissolution/coagulation approach employing the hitherto rarely used TBAF/DMSO/H2O system for cellulose dissolution. Here, we report bioactivity and preliminary hemocompatibility testing of dual-porous cellulose phosphate aerogels (contrasted with the phosphate-free reference) obtained via coagulation (water/ethanol), solvent exchange and scCO2 drying. Deposition of hydroxyapatite from simulated body fluid (7 days of immersion) revealed good bioactivity (1.5-2.2mg Ca2+ per mg scaffold). Incubation of the scCO2-dried and rehydrated scaffolding materials in heparin anticoagulated human whole blood was conducted to study selected parameters of hemostasis (prothrombin F1+2 fragment, PF4, count of thrombocyte-leukocyte conjugates) and inflammatory response (C5a fragment, leukocyte activation marker CD11b). Adhesion of leukocytes on the surface of the incubated substrates was assessed by scanning electron and fluorescence microscopy (DAPI staining). The results suggest that phosphorylation at low DS does not increase platelet activation. However, a significant increase in platelet activation and thrombin formation was observed after a certain fraction of the negative surface charges had been compensated by Ca2+ ions. The combination of both phosphorylation and calcification turned out to be a potent means for controlling the inflammatory response, which was close to baseline level for some of the studied samples.