Superelastic and Arbitrary‐Shaped Graphene Aerogels with Sacrificial Skeleton of Melamine Foam for Varied Applications

Elastic graphene aerogels are lightweight and offer excellent and electrical performance, expanding their significance in many applications. Recently, elastic graphene aerogels have been fabricated via various methods. However, for most reported elastic graphene aerogels, the fabrication processes are complicated and the applications are usually limited by the brittle mechanical properties. Thus, it still remains a challenge to explore facile processes for the fabrication of graphene aerogels with low density and high compressibility. Herein, arbitrary‐shaped, superelastic, and durable graphene aerogels are fabricated using melamine foam as sacrificial skeleton. The resulting graphene aerogels possess high elasticity under compressive stress of 0.556 MPa and compressive strain of 95%. Thanks to the superelasticity, high strength, excellent flexibility, outstanding thermal stability, and good electrical conductivity of graphene aerogels, they can be applied in sorbents and pressure/strain sensors. The as‐assembled graphene aerogels can adsorb various organic solvents at 176–513 g g^?1 depending on the solvent type and density. Moreover, both the squeezing and combustion methods can be adopted for reusing the graphene aerogels. Finally, the graphene aerogels exhibit stable and sensitive current responses, making them the ideal candidates for applications as multifunctional pressure/strain sensors such as wearable devices.     

Optical Design of Silica Aerogels for On-Demand Thermal Management

Silica aerogels, a type of porous material featuring extra low density and thermal conductivity, have drawn increasing interest from both academia and industry owing to their excellent thermal insulation performance. However, thermal insulation is always the single consideration when silica aerogels are used for thermal management. In this study, the on-demand thermal management (ODTM) of silica aerogel with either passive thermal insulation, passive heating, or passive cooling in different environments is revealed. The ODTM behavior of silica aerogels can be simply fulfilled through their optical property variations such as solar light transparency and infrared emissivity, which are controllable via the microstructures of the building blocks and surface composition design. Robust solar heating of 25 °C higher than the ambient in the daytime and sub-ambient cooling of 7 °C at night is achieved with the traditional transparent silica aerogel. Interestingly, sub-ambient cooling of 5 °C in the daytime and a warmer state on cold nights is achieved by modifying its solar transmittance and infrared emissivity. This study guides a comprehensive understanding of the thermal management behavior of silica aerogels and leads to ODTM applications of silica aerogels by tailoring their optical and thermal conductivity properties.     

“Stiff–Soft” Binary Synergistic Aerogels with Superflexibility and High Thermal Insulation Performance

Designing aerogel materials featuring both high thermal insulation property and excellent mechanical robustness is of great interest for applications in superior integrated energy management systems. To meet the above requirements, composite aerogels based on hierarchical “stiff–soft” binary networks are reported, in which secondary mesoporous polymethylsilsesquioxane domains intertwined by bacterial cellulose nanofibrillar networks are connected in tandem. The resulting composite aerogels are characterized by highly porous (93.6%) and nanosized structure with a surface area of 660 m² g^?1, leading to the excellent thermal insulation performance with a low thermal conductivity of 15.3 mW m^?1 K^?1. The integrated “stiff–soft” binary nature also endows the composite aerogels with high flexibility that can conform to various substrates as well as large tensile strength that can withstand more than 2.70 × 10⁴ times its own weight. These composite aerogels show multifunctionality in terms of efficient wearable protection, controllable thermal management, and ultrafast oil/water separation. These favorable multifeatures present composite aerogels ideal for aerospace, industrial, and commercial applications.     

Additive Manufacturing of 3D Aerogels and Porous Scaffolds: A Review

Aerogels are highly porous structures produced by replacing the liquid solvent of a gel with air without causing a collapse in the solid network. Unlike conventional fabrication methods, additive manufacturing (AM) has been applied to fabricate 3D aerogels with customized geometries specific to their applications, designed pore morphologies, multimaterial structures, etc. To date, three major AM technologies (extrusion, inkjet, and stereolithography) followed by a drying process have been proposed to additively manufacture 3D functional aerogels. 3D-printed aerogels and porous scaffolds showed great promise for a variety of applications, including tissue engineering, electrochemical energy storage, controlled drug delivery, sensing, and soft robotics. In this review, the details of steps included in the AM of aerogels and porous scaffolds are discussed, and a general frame is provided for AM of those. Then, the different postprinting processes are addressed to achieve the porosity (after drying); and mechanical strength, functionality, or both (after postdrying thermal or chemical treatments) are provided. Furthermore, the applications of the 3D-printed aerogels/porous scaffolds made from a variety of materials are also highlighted. The review is concluded with the current challenges and an outlook for the next generation of 3D-printed aerogels and porous scaffolds.     

Hierarchical Interface Engineering for Advanced Nanocellulosic Hybrid Aerogels with High Compressibility and Multifunctionality

The hierarchical combination of mineral and biopolymer building blocks is advantageous for the notable properties of structural materials. Integrating silane and cellulose nanofibers into high-performance hybrid aerogels is promising yet remains challenging due to the unsatisfied interface connections. Here, an interfacial engineering strategy is introduced via freeze–drying-induced wetting and mineralization to reinforce the hierarchical porous cellulose network, resulting in mineral-coated nanocellulose hybrid aerogels in a simple and consecutive bottom-up assembly process. With optimized multiscale interfacial engineering between the stiff and soft components, the resulting cellulose-based hybrid aerogels are endowed with lightweight (>0.7 mg cm⁻³), superior enhanced mechanical compressibility (>99% strain) within a wide temperature range, as well as super-hydrophobicity (≈168°) and moisture stability under high humidity (95% relative humidity). Benefiting from these superior characters, the multifunctional hybrid aerogels as effective oil/water absorbents with excellent recyclability, thermal insulators in extreme conditions, and sensitive strain sensors are demonstrated. This assembly approach with optimized interfacial features is scalable and efficient, affording high-performance cellulose-based aerogels for various applications.     

M13 Virus Aerogels as a Scaffold for Functional Inorganic Materials

The filamentous M13 viruses are widely used as a bio‐template to assemble many different functional structures. In this work, based on its shape anisotropy, reasonable aspect ratio (length to diameter of ≈130), and low density, freestanding, bulk 3D aerogels are assembled from M13 for the first time. These ultralight porous structures demonstrate excellent mechanical properties with elastic behavior up to 90% compression. Furthermore, as the genome of M13 virus can be rationally engineered so that proteins on its capsid or ends can specifically bind to various inorganic materials, aerogels made from inorganic‐complexed M13 structures with versatile functionalities are also developed. As examples for mono‐ and multi‐component structures, M13‐Ru and M13‐CoFe₂O₄ are explored in this work. This method enables the production of a wide variety of freestanding inorganic material aerogels with extensive opportunities for bio‐scaffolds, energy storage, thermoelectrics, catalysis, hydrogen storage applications, etc., in the future.     

Photoswitchable Superabsorbency Based on Nanocellulose Aerogels

Chemical vapor deposition of a thin titanium dioxide (TiO₂) film on lightweight native nanocellulose aerogels offers a novel type of functional material that shows photoswitching between water‐superabsorbent and water‐repellent states. Cellulose nanofibrils (diameters in the range of 5–20 nm) with native crystalline internal structures are topical due to their attractive mechanical properties, and they have become relevant for applications due to the recent progress in the methods of their preparation. Highly porous, nanocellulose aerogels are here first formed by freeze‐drying from the corresponding aqueous gels. Well‐defined, nearly conformal TiO₂ coatings with thicknesses of about 7 nm are prepared by chemical vapor deposition on the aerogel skeleton. Weighing shows that such TiO₂‐coated aerogel specimens essentially do not absorb water upon immersion, which is also evidenced by a high contact angle for water of 140° on the surface. Upon UV illumination, they absorb water 16 times their own weight and show a vanishing contact angle on the surface, allowing them to be denoted as superabsorbents. Recovery of the original absorption and wetting properties occurs upon storage in the dark. That the cellulose nanofibrils spontaneously aggregate into porous sheets of different length scales during freeze‐drying is relevant: in the water‐repellent state they may stabilize air pockets, as evidenced by a high contact angle, in the superabsorbent state they facilitate rapid water‐spreading into the aerogel cavities by capillary effects. The TiO₂‐coated nanocellulose aerogels also show photo‐oxidative decomposition, i.e., photocatalytic activity, which, in combination with the porous structure, is interesting for applications such as water purification. It is expected that the present dynamic, externally controlled, organic/inorganic aerogels will open technically relevant approaches for various applications.     

Multiscale Assembly of Superinsulating Silica Aerogels Within Silylated Nanocellulosic Scaffolds: Improved Mechanical Properties Promoted by Nanoscale Chemical Compatibilization

Silica aerogels are amongst the lightest mesoporous solids known and well recognized for their superinsulating properties, but the weak mechanical properties of the inorganic network structure has often narrowed their field of application. Here, the inherent brittleness of dried inorganic gels is tackled through the elaboration of a strong mesoporous silica aerogel interpenetrated with a silylated nanocellulosic scaffold. To this avail, a functionalized scaffold is synthesized by freeze‐drying an aqueous suspension of nanofibrillated cellulose (NFC)—a bio‐based nanomaterial mechanically isolated from renewable resources—in the presence of methyltrimethoxysilane sol. The silylated NFC scaffold displays a high porosity (>98%), high flexibility, and reduced thermal conductivity (λ) compared with classical cellulosic structures. The polysiloxane layer decorating the nanocellulosic scaffold is exploited to promote the attachment of the mesoporous silica matrix onto the nanofibrillated cellulose scaffold (NFCS), leading to a reinforced silica hybrid aerogel with improved thermomechanical properties. The highly porous (>93%) silica‐NFC hybrids displays meso‐ and macroporosity with pore diameters controllable by the NFCS mass fraction, reduced linear shrinkage, improved compressive properties (55% and 126% increase in Young's modulus and tensile strength, respectively), while maintaining superinsulating properties (λ ≤ 20 mW (m K)^–1). This study details a new direction for the synthesis of multiscale hybrid silica aerogel structures with tailored properties through the use of alkyltrialkoxysilane prefunctionalized nanocellulosic scaffolds.     

Borax‐Mediated Formation of Carbon Aerogels from Glucose

Hierarchically structured carbon aerogels are produced in a simple, rapid, efficient, and sustainable hydrothermal approach, using only glucose as the carbon precursor. Using sodium borate (borax) as a novel complex structure directing agent nanostructured, carbon monoliths, structurally similar to the well‐known sol‐gel monoliths made of silica are obtained. Experimental results indicate the acetalization reaction of monosaccharides with their dehydration product hydroxymethylfurfural to be very important and inhibiting in the process of hydrothermal carbonization. Addition of borax, leads to a competitive complexation of diols, resulting in promising secondary catalytic effect with regard to carbon yield. Accordingly, it is shown that the sugar:borax ratio directs the primary carbon nanoparticle size into the sub ?50 nm range, while their spinodal destabilization ultimately results in the controlled aggregation of carbonaceous particles leading to the formation of monoliths in a simple one step hydrothermal process. Post‐synthesis thermal carbonization is also used to increase surface area to the medium‐high range, introducing electric conductivity into the carbon monoliths. The resulting materials are promising candidates for applications in flash chromatography, for fast adsorption/purifications, and as porous conductive electrodes.     

Robust Carbonaceous Nanofiber Aerogels from All Biomass Precursors

Aerogels, a type of fascinating material with very low density and high surface area, show many unique properties and unlimited applications. To boost their practical applications, it is necessary to develop efficient, controllable, and low-cost methods to produce high-performance aerogels on a large-scale, preferably in a sustainable way. Here, a general strategy is reported for controllable fabrication of a family of carbonaceous nanofiber aerogels (CNFAs) by biomass-derived nanofibers template-directed hydrothermal carbonization method. Abundant functional groups are exposed on the surface of the prepared carbonaceous nanofibers. Importantly, in contrast to traditional nature biopolymer-based aerogels, a superior combination of good recoverability and high strength is achieved for the CNFAs by adjusting the synthetic parameters. The successful synthesis of such fascinating materials provides an excellent platform for design and construction of devices for fast water treatment. The synthetic strategy and sustainable concept presented in this work will open a new way to prepare advanced aerogels with unique properties for wide applications.     

Mechanical and Thermal Management Characteristics of Ultrahigh Surface Area Single‐Walled Carbon Nanotube Aerogels

Lightweight aerogels with large specific surface area (SSA) have numerous applications. Free‐standing aerogels are created from single‐walled carbon nanotubes (SWCNTs), and their SSA and pore characteristics, electrical conductivity, mechanical properties, and thermal management attributes are determined. The SSA of the aerogels is extraordinarily high and approaches 1291 m² g^?1 at a density of 7.3 mg mL^?1, which is close to the theoretical limit (≈1315 m² g^?1). Mechanical characterization shows that these aerogels have open‐cell structures and their Young's moduli are higher than other aerogels at comparable density. The aerogels also enhance heat transfer in a forced convective process by ≈85%, presumably due to their large porosity and surface area.     

Ambient‐Dried, 3D‐Printable and Electrically Conducting Cellulose Nanofiber Aerogels by Inclusion of Functional Polymers

This study presents a novel, green, and efficient way of preparing crosslinked aerogels from cellulose nanofibers (CNFs) and alginate using non‐covalent chemistry. This new process can ultimately facilitate the fast, continuous, and large‐scale production of porous, light‐weight materials as it does not require freeze‐drying, supercritical CO₂ drying, or any environmentally harmful crosslinking chemistries. The reported preparation procedure relies solely on the successive freezing, solvent‐exchange, and ambient drying of composite CNF‐alginate gels. The presented findings suggest that a highly‐porous structure can be preserved throughout the process by simply controlling the ionic strength of the gel. Aerogels with tunable densities (23–38 kg m^?3) and compressive moduli (97–275 kPa) can be prepared by using different CNF concentrations. These low‐density networks have a unique combination of formability (using molding or 3D‐printing) and wet‐stability (when ion exchanged to calcium ions). To demonstrate their use in advanced wet applications, the printed aerogels are functionalized with very high loadings of conducting poly(3,4‐ethylenedioxythiophene):tosylate (PEDOT:TOS) polymer by using a novel in situ polymerization approach. In‐depth material characterization reveals that these aerogels have the potential to be used in not only energy storage applications (specific capacitance of 78 F g^?1), but also as mechanical‐strain and humidity sensors.     

Strong,Machinable Carbon Aerogels for High Performance Supercapacitors

Designing macroscopic, 3D porous conductive materials with high mechanical strength is of great importance in many fields, including energy storage, catalysis, etc. This study reports a novel approach to fabricate polyaniline‐coated 3D carbon x‐aerogels, a special type of aerogels with mechanically strong, highly cross‐linked structure that allows the originally brittle aerogels machinable. This approach is accomplished by introducing a small amount of graphene into the sol–gel process of resorcinol and formaldehyde, followed by physical activation and subsequent cross‐linking with polyaniline via electropolymerization. The resulting x‐aerogels are not only porous and conductive, but also mechanically robust with high compressibility and fast recovery. The strong combination of these properties makes the x‐aerogels promising for high performance supercapacitors that are designed to provide additional functionality for wearable and portable electronics. Such multi‐functionality leads to a significant increase in electrochemical performance, in particular high volumetric capacitance, which results from the more densely packed electroactive structure in three dimensions. More importantly, monoliths of carbon x‐aerogels are machinable into thin slices without losing their properties, thus enabling effective integration into devices with different sizes and shapes.     

Hyperelastic,Robust, Fire-Safe Multifunctional MXene Aerogels with Unprecedented Electromagnetic Interference Shielding Efficiency

MXene aerogels have shown great potential for many important functional applications, in particular electromagnetic interference (EMI) shielding. However, it has been a grand challenge to create mechanically hyperelastic, air-stable, and durable MXene aerogels for enabling effective EMI protection at low concentrations due to the difficulties in achieving tailorable porous structures, excellent mechanical elasticity, and desired antioxidation capabilities of MXene in air. Here, a facile strategy for fabricating MXene composite aerogels by co-assembling MXene and cellulose nanofibers during freeze-drying followed by surface encapsulation with fire-retardant thermoplastic polyurethane (TPU) is reported. Because of the maximum utilization of pore structures of MXene, and conductive loss enhanced by multiple internal reflections, as-prepared aerogel with 3.14 wt% of MXene exhibits an exceptionally high EMI shielding effectiveness of 93.5 dB, and an ultra-high MXene utilization efficiency of 2977.71 dB g g⁻¹, tripling the values in previous works. Owing to the presence of multiple hydrogen bonding and the TPU elastomer, the aerogel exhibits a hyperelastic feature with additional strength, excellent stability, superior durability, and high fire safety. This study provides a facile strategy for creating multifunctional aerogels with great potential for applications in EMI protection, wearable devices, thermal management, pressure sensing, and intelligent fire monitoring.     

Flexible,Highly Graphitized Carbon Aerogels Based on Bacterial Cellulose/Lignin: Catalyst‐Free Synthesis and its Application in Energy Storage Devices

Currently, most carbon aerogels are based on carbon nanotubes (CNTs) or graphene, which are produced through a catalyst‐assisted chemical vapor deposition method. Biomass based organic aerogels and carbon aerogels, featuring low cost, high scalability, and small environmental footprint, represent an important new research direction in (carbon) aerogel development. Cellulose and lignin are the two most abundant natural polymers in the world, and the aerogels based on them are very promising. Classic silicon aerogels and available organic resorcinol–formaldehyde (RF) or lignin–resorcinol–formaldehyde (LRF) aerogels are brittle and fragile; toughening of the aerogels is highly desired to expand their applications. This study reports the first attempt to toughen the intrinsically brittle LRF aerogel and carbon aerogel using bacterial cellulose. The facile process is catalyst‐free and cost‐effective. The toughened carbon aerogels, consisting of blackberry‐like, core–shell structured, and highly graphitized carbon nanofibers, are able to undergo at least 20% reversible compressive deformation. Due to their unique nanostructure and large mesopore population, the carbon materials exhibit an areal capacitance higher than most of the reported values in the literature. This property makes them suitable candidates for flexible solid‐state energy storage devices. Besides energy storage, the conductive interconnected nanoporous structure can also find applications in oil/water separation, catalyst supports, sensors, and so forth.     

Mixed Aerogels from Au and CdTe Nanoparticles

Mixed metal–semiconductor nanocrystal aerogels are fabricated, which are light‐emitting and highly porous macroscopic monoliths. Thiol‐stabilized CdTe and Au nanoparticles from aqueous synthesis act as building blocks for the hybrid material. The Au colloids undergo a surface‐modification to enhance the particle stability and achieve thiol functionalities. A photochemical treatment is applied for the gelation process which is found to be reversible by subsequent addition of thiol molecules. Via supercritical drying aerogels are formed. The variation of the initial CdTe to Au nanoparticle ratio permits a facile tuning of the content and the properties of the resulting aerogels. The obtained structures were characterized by means of optical spectroscopy, electron microscopy, elemental analysis, and nitrogen physisorption.     

Superelastic and Ultralight Aerogel Assembled from Hemp Microfibers

Aerogels with both high elastic strain and fast shape recovery after compression have broad application potentials as thermal regulation, absorbents, and electrical devices. However, creating such aerogels from cellulosic materials requires complicated preparation processes. Herein, a simple strategy for scalable production of hemp microfibers using a top-down method is reported, which can further be assembled into aerogels with interconnected porous structures via ice-templating technique. With density as low as 2.1 mg cm⁻³, these aerogels demonstrate isotropic superelasticity, as exhibited by their fast shape restoration from over 80% compressive strain. Due to the high porosity (99.87%) and structural tortuosity, these aerogels show a low thermal conductivity of 0.0215 ± 0.0002 W m⁻¹ K⁻¹, suggesting their potential in thermal insulation application. Certain hydrophobic modification using silane derivative further endows these aerogels with reduced water affinity. Overall, the proposed strategy to prepare bio-based microfibers using scalable technology, as well as the assembled aerogels, provides new insights into the design and fabrication of multifunctional bio-based aerogels for value-added applications.     

Reversibly Compressible,Highly Elastic,and Durable Graphene Aerogels for Energy Storage Devices under Limiting Conditions

High porosity combined with mechanical durability in conductive materials is in high demand for special applications in energy storage under limiting conditions, and it is fundamentally important for establishing a relationship between the structure/chemistry of these materials and their properties. Herein, polymer‐assisted self‐assembly and cross‐linking are combined for reduced graphene oxide (rGO)‐based aerogels with reversible compressibility, high elasticity, and extreme durability. The strong interplay of cross‐linked rGO (x‐rGO) aerogels results in high porosity and low density due to the re‐stacking inhibition and steric hinderance of the polymer chains, yet it makes mechanical durability and structural bicontinuity possible even under compressive strains because of the coupling of directional x‐rGO networks with polymer viscoelasticity. The x‐rGO aerogels retain >140% and >1400% increases in the gravimetric and volumetric capacitances, respectively, at 90% compressive strain, showing reversible change and stability of the volumetric capacitance under both static and dynamic compressions; this makes them applicable to energy storage devices whose volume and mass must be limited.     

Recent Advances in MXene-Based Aerogels: Fabrication,Performance and Application

As one of the “miracle materials” in the 21st century, aerogels with ultra-low weight and remarkable mechanical performance have emerged and shown incredible immunity to harsh working environments, attracting substantial research interests across a wide range of areas. Recently, exploitation of MXene nanosheets into aerogels represents a new research focus in the field of materials science, on account of their unique structures and outstanding properties. In this review, the aim is to provide a timely and insightful overview for the recent advances in the fabrication, performance, and application of MXene-based aerogels. The main strategies for constructing MXene-based aerogels, directly from MXene-dispersion or in the presence of other functional components, are summarized. Furthermore, the desirable performance of MXene-based aerogels and their related applications in the areas including electromagnetic management, sensors, solar steam generators, and energy storage are highlighted. A thorough investigation and comparison of their mechanical, electrical, sensing, and other properties are performed to understand the structure-property relationships. At last, this study is concluded with summary and outlook section on the future development as well as challenges that remained, thus bringing new research opportunities for the material engineering and functional application of MXene-based aerogels.     

Ultra‐High Surface Area Nitrogen‐Doped Carbon Aerogels Derived From a Schiff‐Base Porous Organic Polymer Aerogel for CO2 Storage and Supercapacitors

Nitrogen‐doped carbon aerogels (NCAs) have received great attention for a wide range of applications, from thermal electronics to waste water purification, heavy metal or gas adsorption, energy storage, and catalyst supports. Herein NCAs are developed via the synthesis of a Schiff‐base porous organic polymer aerogel followed by pyrolysis. By controlling the pyrolysis temperature, the polymer aerogel can be simply converted into porous NCAs with a low bulk density (5 mg cm^?3), high surface area (2356 m² g^?1), and high bulk porosity (70%). The NCAs containing 1.8–5.3 wt% N atoms exhibit remarkable CO₂ uptake capacities (6.1 mmol g^?1 at 273 K and 1 bar, 33.1 mmol g^?1 at 323 K and 30 bar) and high ideal adsorption solution theory selectivity (47.8) at ambient pressure. Supercapacitors fabricated with NCAs display high specific capacitance (300 F g^?1 at 0.5 A g^?1), fast rate (charge to 221 F g^?1 within only 17 s), and high stability (retained >98% capacity after 5000 cycles). Asymmetric supercapacitors assembled with NCAs also show high energy density and power density with maximal values of 30.5 Wh kg^?1 and 7088 W kg^?1, respectively. The outstanding CO₂ uptake and energy storage abilities are attributed to the ultra‐high surface area, N‐doping, conductivity, and rigidity of NCA frameworks.