Multiphase Symbiotic Engineered Elastic Ceramic-Carbon Aerogels with Advanced Thermal Protection in Extreme Oxidative Environments.

Elastic aerogels can dissipate aerodynamic forces and thermal stresses by reversible slipping or deforming to avoid sudden failure caused by stress concentration, making them the most promising candidates for thermal protection in aerospace applications. However, existing elastic aerogels face difficulties achieving reliable protection above 1500 °C in aerobic environments due to their poor thermomechanical stability and significantly increased thermal conductivity at elevated temperatures. Here, a multiphase sequence and multiscale structural engineering strategy is proposed to synthesize mullite-carbon hybrid nanofibrous aerogels. The heterogeneous symbiotic effect between components simultaneously inhibits ceramic crystalline coarsening and carbon thermal etching, thus ensuring the thermal stability of the nanofiber building blocks. Efficient load transfer and high interfacial thermal resistance at crystalline-amorphous phase boundaries on the microscopic scale, coupled with mesoscale lamellar cellular and locally closed-pore structures, achieve rapid stress dissipation and thermal energy attenuation in aerogels. This robust thermal protection material system is compatible with ultralight density (30 mg cm-3), reversible compression strain of 60%, extraordinary thermomechanical stability (up to 1600 °C in oxidative environments), and ultralow thermal conductivity (50.58 mW m-1 K-1 at 300 °C), offering new options and possibilities to cope with the harsh operating environments faced by space exploration.

Ceramic Meta-Aerogel with Thermal Superinsulation up to 1700 °C Constructed by Self-Crosslinked Nanofibrous Network via Reaction Electrospinning.

Thermal insulation under extreme conditions requires the materials to be capable of withstanding complex thermo-mechanical stress, significant gradient temperature transition, and high-frequency thermal shock. The excellent structural and functional properties of ceramic aerogels make them attractive for thermal insulation. However, in extremely high-temperature environments (above 1500 °C), they typically exhibit limited insulation capacity and thermo-mechanical stability, which may lead to catastrophic accidents, and this problem is never effectively addressed. Here, a novel ceramic meta-aerogel constructed from a crosslinked nanofiber network using a reaction electrospinning strategy, which ensures excellent thermo-mechanical stability and superinsulation under extreme conditions, is designed. The ceramic meta-aerogel has an ultralow thermal conductivity of 0.027 W m-1 k-1, and the cold surface temperature is only 303 °C in a 1700 °C high-temperature environment. After undergoing a significant gradient temperature transition from liquid nitrogen to 1700 °C flame burning, the ceramic meta-aerogel can still withstand thousands of shears, flexures, compressions, and other complex forms of mechanical action without structural collapse. This work provides a new insight for developing ceramic aerogels that can be used for a long period in extremely high-temperature environments.

Building-Envelope-Inspired, Thermomechanically Robust All-Fiber Ceramic Meta-Aerogel for Temperature-Controlled Dominant Infrared Camouflage.

The unsatisfactory properties of ceramic aerogels when subjected to thermal shock, such as strength degradation and structural collapse, render them unsuitable for use at large thermal gradients or prolonged exposure to extreme temperatures. Here, a building-envelope-inspired design for fabricating a thermomechanically robust all-fiber ceramic meta-aerogel with interlocked fibrous interfaces and an interwoven cellular structure in the orthogonal directions is presented, which is achieved through a two-stage physical and chemical process. Inspired by the reinforced concrete building envelope, a solid foundation composed of fibrous frames is constructed and enhanced through supramolecular in situ self-assembly to achieve high compressibility, retaining over 90% of maximum stress under a considerable compressive strain of 50% for 10 000 cycles, and showing temperature-invariance when compressed at 60% strain within the range of -100 to 500 °C. As a result of its distinct response to oscillation tolerance coupled with elastic recovery, the all-fiber ceramic meta-aerogel exhibits exceptional suitability for thermal shock resistance and infrared camouflage performance in cold (-196 °C) and hot (1300 °C) fields. This study provides an opportunity for developing ceramic aerogels for effective thermal management under extreme conditions.

Enhanced N2 Adsorption and Activation by Combining Re Clusters and In Vacancies as Dual Sites for Efficient and Selective Electrochemical NH3 Synthesis.

The electrochemical N2 reduction reaction (NRR) is a green and energy-saving sustainable technology for NH3 production. However, high activity and high selectivity can hardly be achieved in the same catalyst, which severely restricts the development of the electrochemical NRR. In2Se3 with partially occupied p-orbitals can suppress the H2 evolution reaction (HER), which shows excellent selectivity in the electrochemical NRR. The presence of VIn can simultaneously provide active sites and confine Re clusters through strong charge transfer. Additionally, well-isolated Re clusters stabilized on In2Se3 by the confinement effect of VIn result in Re-VIn active sites with maximum availability. By combining Re clusters and VIn as dual sites for spontaneous N2 adsorption and activation, the electrochemical NRR performance is enhanced significantly. As a result, the Re-In2Se3-VIn/CC catalyst delivers a high NH3 yield rate (26.63 µg h-1 cm-2) and high FEs (30.8%) at -0.5 V vs RHE.

Multiscale Interpenetrated/Interconnected Network Design Confers All-Carbon Aerogels with Unprecedented Thermomechanical Properties for Thermal Insulation under Extreme Environments.

With ultralight weight, low thermal conductivity, and extraordinary high-temperature resistance, carbon aerogels hold tremendous potential against severe thermal threats encountered by hypersonic vehicles during the in-orbit operation and re-entry process. However, current 3D aerogels are plagued by irreconcilable contradictions between adiabatic and mechanical performance due to monotonicity of the building blocks or uncontrollable assembly behavior. Herein, a spatially confined assembly strategy of multiscale low-dimensional nanocarbons is reported to decouple the stress and heat transfer. The nanofiber framework, a basis for transferring the loading strain, is covered by a continuous thin-film-like layer formed by the aggregation of nanoparticles, which in combination serve as the fundamental structural units for generating an elastic behavior while yielding compartments in aerogels to suppress the gaseous fluid thermal diffusion within distinct partitions. The resulting all-carbon aerogels with a hierarchical cellular structure and quasi-closed cell walls achieve the best thermomechanical and insulation trade-off, exhibiting flyweight density (24 mg cm-3 ), temperature-constant compressibility (-196-1600 °C), and a low thermal conductivity of 0.04 829 W m-1 K-1 at 300 °C. This strategy provides a remarkable thermal protection material in hostile environments for future aerospace exploration.

Way to a Library of Ti-Series Oxide Nanofiber Sponges that are Highly Stretchable, Compressible, and Bendable.

Ti-series oxide ceramics in the form of aerogels, such as TiO2, SrTiO3, BaTiO3, and CaCu3Ti4O12, hold tremendous potential as functional materials owing to their excellent optical, dielectric, and catalytic properties. Unfortunately, these inorganic aerogels are usually brittle and prone to pulverization owing to weak inter-particulate interactions, resulting in restricted application performance and serious health risks. Herein, a novel strategy is reported to synthesize an elastic form of an aerogel-like, highly porous structure, in which activity-switchable Ti-series oxide sols transform from the metastable state to the active state during electrospinning, resulting in condensation and solidification at the whipping stage to obtain curled nanofibers. These curled nanofibers are further entangled when flying in the air to form a physically interlocked, elastic network mimicking the microstructure of high-elasticity hydrogels. This strategy provides a library of Ti-series oxide nanofiber sponges with unprecedented stretchability, compressibility, and bendability, possessing extensive opportunities for greener, safer, and broader applications as integrated or wearable functional devices. As a proof-of-concept demonstration, a new, elastic form of TiO2, composed of both "white" and "black" TiO2 nanofiber sponges, is constructed as spontaneous air-conditioning textiles in smart clothing, buildings, and vehicles, with unique bidirectional regulation of radiative cooling in summer and solar heating in winter.

Multiscale Synergetic Bandgap/Structure Engineering in Semiconductor Nanofibrous Aerogels for Enhanced Solar Evaporation.

Solar-driven interface evaporation has been identified as a sustainable seawater desalination and water purification technology. Nonetheless, the evaporation performance is still restricted by salt deposition and heat loss owing to weak solar spectrum absorption, tortuous channels, and limited plane area of conventional photothermal material. Herein, the semiconductor nanofibrous aerogels with a narrow bandgap, vertically aligned channels, and a conical architecture are constructed by the multiscale synergetic engineering strategy, encompassing bandgap engineering at the atomic scale and structure engineering at the nano-micro scale. As a proof-of-concept demonstration, a Co-doped MoS2 nanofibrous aerogel is synthesized, which exhibits the entire solar absorption, superhydrophilic, and excellent thermal insulation, achieving a net evaporation rate of 1.62 kg m-2 h-1 under 1 sun irradiation, as well as a synergistically efficient dye ion adsorption function. This work opens up new possibilities for the development of solar evaporators for practical applications in clean water production.

Scalable Synthesis of Flexible Single-Atom Monolithic Catalysts for High-Efficiency, Durable CO Oxidation at Low Temperature.

The creation of single-atom catalysts in a large-size, high-yield, and stable form represents an important direction for high-efficiency industrial catalysis in the future. Herein, we report a strategy to synthesize flexible single-atom monolithic catalysts (SAMCs) based on the hierarchical 3D assembly of single-atom-loaded oxide ceramic nanofibers. The nanofibers, which can be produced in a continuous and scalable manner, serve as an ideal support for single atoms spontaneously and almost completely exposed at the surface through the Kirkendall effect-enabled in situ ion migration during the spinning process, resulting in both high yield and large loading quantity. Moreover, the hierarchical 3D assembly of these nanofibers into a porous, flexible structure endows the SAMCs with the advantages of sufficient infiltration and oscillation tolerance when faced with high-throughput gaseous media, leading to both high catalytic efficiency and excellent durability. As a proof-of-concept demonstration, a Pt SAMC is synthesized, which exhibits 100% CO oxidation at low temperature (∼170 °C), excellent invariance toward high-frequency (10 Hz) oscillation, and high structural stability from 25 to 300 °C. This work is beneficial for the large-scale production of SAMCs in broad industrial applications.

Inhibited Grain Growth Through Phase Transition Modulation Enables Excellent Mechanical Properties in Oxide Ceramic Nanofibers up to 1700 °C.

Oxide ceramics are widely used as thermal protection materials due to their excellent structural properties and earth abundance. However, in extremely high-temperature environments (above 1500 °C), the explosive growth of grain size causes irreversible damage to the microstructure of oxide ceramics, thus exhibiting poor thermomechanical stability. This problem, which may lead to catastrophic accidents, remains a great challenge for oxide ceramic materials. Here, a novel strategy of phase transition modulation is proposed to control the grain growth at high temperatures in oxide ceramic nanofibers, realizing effective regulation of the crystalline forms as well as the size uniformity of primary grains, and thus suppressing the malignant growth of the grains. The resulting oxide ceramic nanofibers have excellent mechanical strength and flexibility, delivering an average tensile strength as high as 1.02 GPa after being exposed to 1700 °C for 30 min, and can withstand thousands of flexural cycles without obvious damage. This work may provide new insight into the development of advanced oxide ceramic materials that can serve in extremely high-temperature environments with long-term durability.

High Toughness Combined with High Strength in Oxide Ceramic Nanofibers.

Traditional oxide ceramics are inherently brittle and highly sensitive to defects, making them vulnerable to failure under external stress. As such, endowing these materials with high strength and high toughness simultaneously is crucial to improve their performance in most safety-critical applications. Fibrillation of the ceramic materials and further refinement of the fiber diameter, as realized by electrospinning, are expected to achieve the transformation from brittleness to flexibility owing to the structural uniqueness. Currently, the synthesis of electrospun oxide ceramic nanofibers must rely on an organic polymer template to regulate the spinnability of the inorganic sol, whose thermal decomposition during ceramization will inevitably lead to pore defects, and seriously weaken the mechanical properties of the final nanofibers. Here, a self-templated electrospinning strategy is proposed for the formation of oxide ceramic nanofibers without adding any organic polymer template. An example is given to show that individual silica nanofibers have an ideally homogeneous, dense, and defect-free structure, with tensile strength as high as 1.41 GPa and toughness up to 34.29 MJ m-3 , both of which are far superior to the counterparts prepared by polymer-templated electrospinning. This work provides a new strategy to develop oxide ceramic materials that are strong and tough.

Fibrous MXene Aerogels with Tunable Pore Structures for High-Efficiency Desalination of Contaminated Seawater.

The seawater desalination based on solar-driven interfacial evaporation has emerged as a promising technique to alleviate the global crisis on freshwater shortage. However, achieving high desalination performance on actual, oil-contaminated seawater remains a critical challenge, because the transport channels and evaporation interfaces of the current solar evaporators are easily blocked by the oil slicks, resulting in undermined evaporation rate and conversion efficiency. Herein, we propose a facile strategy for fabricating a modularized solar evaporator based on flexible MXene aerogels with arbitrarily tunable, highly ordered cellular/lamellar pore structures for high-efficiency oil interception and desalination. The core design is the creation of 1D fibrous MXenes with sufficiently large aspect ratios, whose superior flexibility and plentiful link forms lay the basis for controllable 3D assembly into more complicated pore structures. The cellular pore structure is responsible for effective contaminants rejection due to the multi-sieving effect achieved by the omnipresent, isotropic wall apertures together with underwater superhydrophobicity, while the lamellar pore structure is favorable for rapid evaporation due to the presence of continuous, large-area evaporation channels. The modularized solar evaporator delivers the best evaporation rate (1.48 kg m-2 h-1) and conversion efficiency (92.08%) among all MXene-based desalination materials on oil-contaminated seawater.

Complementary Design in Multicomponent Electrocatalysts for Electrochemical Nitrogen Reduction: Beyond the Leverage in Activity and Selectivity.

Electrochemical nitrogen reduction reaction (eNRR) is promising in place of the Haber-Bosch process for artificial N2 fixation. However, the high activity and selectivity of eNRR are challenging to achieve simultaneously due to the scaling relations. Such "leverage" between activity and selectivity has severely restricted eNRR. To overcome this bottleneck, the complementary design of electronic structures in multicomponent electrocatalysts has been recently pursued, aiming to maximize the advantages of each component and optimize the multistep reactions, which has stood at the cutting edge in this aspect. Here, we present a minireview of the design, performance, and mechanism of multicomponent electrocatalysts with complementary electronic structures. We particularly emphasize the interactions between N2 and elements from d-, p-, and s-blocks, which are essential for understanding how these electrocatalysts are beyond the "leverage" between activity and selectivity.

From 1D Nanofibers to 3D Nanofibrous Aerogels: A Marvellous Evolution of Electrospun SiO2 Nanofibers for Emerging Applications.

One-dimensional (1D) SiO2 nanofibers (SNFs), one of the most popular inorganic nanomaterials, have aroused widespread attention because of their excellent chemical stability, as well as unique optical and thermal characteristics. Electrospinning is a straightforward and versatile method to prepare 1D SNFs with programmable structures, manageable dimensions, and modifiable properties, which hold great potential in many cutting-edge applications including aerospace, nanodevice, and energy. In this review, substantial advances in the structural design, controllable synthesis, and multifunctional applications of electrospun SNFs are highlighted. We begin with a brief introduction to the fundamental principles, available raw materials, and typical apparatus of electrospun SNFs. We then discuss the strategies for preparing SNFs with diverse structures in detail, especially stressing the newly emerging three-dimensional SiO2 nanofibrous aerogels. We continue with focus on major breakthroughs about brittleness-to-flexibility transition of SNFs and the means to achieve their mechanical reinforcement. In addition, we showcase recent applications enabled by electrospun SNFs, with particular emphasis on physical protection, health care and water treatment. In the end, we summarize this review and provide some perspectives on the future development direction of electrospun SNFs.

Direct synthesis of highly stretchable ceramic nanofibrous aerogels via 3D reaction electrospinning.

Ceramic aerogels are attractive for many applications due to their ultralow density, high porosity, and multifunctionality but are limited by the typical trade-off relationship between mechanical properties and thermal stability when used in extreme environments. In this work, we design and synthesize ceramic nanofibrous aerogels with three-dimensional (3D) interwoven crimped-nanofibre structures that endow the aerogels with superior mechanical performances and high thermal stability. These ceramic aerogels are synthesized by a direct and facile route, 3D reaction electrospinning. They display robust structural stability with structure-derived mechanical ultra-stretchability up to 100% tensile strain and superior restoring capacity up to 40% tensile strain, 95% bending strain and 60% compressive strain, high thermal stability from -196 to 1400 °C, repeatable stretchability at working temperatures up to 1300 °C, and a low thermal conductivity of 0.0228 W m-1 K-1 in air. This work would enable the innovative design of high-performance ceramic aerogels for various applications.

Highly Active and Selective Electroreduction of N2 by the Catalysis of Ga Single Atoms Stabilized on Amorphous TiO2 Nanofibers.

The electroreduction of N2 under ambient conditions has emerged as one of the most promising technologies in chemistry, since it is a greener way to make NH3 than the traditional Haber-Bosch process. However, it is greatly challenged with a low NH3 yield and faradaic efficiency (FE) because of the lack of highly active and selective catalysts. Inherently, transition (d-block) metals suffer from inferior selectivity due to fierce competition from H2 evolution, while post-transition (p-block) metals exhibit poor activity due to insufficient "π back-donation" behavior. Considering their distinct yet complementary electronic structures, here we propose a strategy to tackle the activity and selectivity challenge through the atomic dispersion of p-block metal on an all-amorphous transition-metal matrix. To address the activity issue, lotus-root-like amorphous TiO2 nanofibers are synthesized which, different from vacancy-engineered TiO2 nanocrystals reported previously, possess abundant intrinsic oxygen vacancies (VO) together with under-coordinated dangling bonds in nature, resulting in significantly enhanced N2 activation and electron transport capacity. To address the selectivity issue, well-isolated single atoms (SAs) of Ga are successfully synthesized through the confinement effect of VO, resulting in Ga-VO reactive sites with the maximum availability. It is revealed by density functional theory calculations that Ga SAs are favorable for the selective adsorption of N2 at the catalyst surface, while VO can facilitate N2 activation and reduction subsequently. Benefiting from this coupled activity/selectivity design, high NH3 yield (24.47 µg h-1 mg-1) and FE (48.64%) are achieved at an extremely low overpotential of -0.1 V vs RHE.

Conductive and Elastic TiO2 Nanofibrous Aerogels: A New Concept toward Self-Supported Electrocatalysts with Superior Activity and Durability.

Recently, various titanium dioxide (TiO2 ) nanostructures have received increasing attention in the fields of energy conversion and storage owing to their electrochemical properties. However, these particulate nanomaterials exclusively exist in the powder form, which may cause health risks and environmental hazards. Herein we report a novel, highly elastic bulk form of TiO2 for safe use and easy recycling. Specifically, TiO2 nanofibrous aerogels (NAs) consisting of resiliently bonded, flexible TiO2 nanofibers are constructed, which have an ultralow bulk density, ultrahigh porosity, and excellent elasticity. To promote charge transfer, they are subjected to lithium reduction to generate abundant oxygen vacancies, which can modulate the electronic structure of TiO2 , resulting in a conductivity up to 38.2 mS cm-1 . As a proof-of-concept demonstration, the conductive and elastic TiO2 NAs serve as a new type of self-supported electrocatalyst for ambient nitrogen fixation, achieving an ammonia yield of 4.19×10-10  mol s-1 cm-2 and a Faradaic efficiency of 20.3 %. The origin of the electrocatalytic activity is revealed by DFT calculations.

P-doped WO3 flowers fixed on a TiO2 nanofibrous membrane for enhanced electroreduction of N2.

Herein, nanoneedle-constructed WO3 flowers are prepared by hydrothermal synthesis, which are characterized by a large surface area leading to abundant active sites. Additionally, P doping is employed as an effective way to generate charge imbalance and induce more empty d-orbitals around W6+, thus facilitating the adsorption of N2 molecules. Moreover, a flexible TiO2 nanofibrous membrane is used as an electrocatalytically active matrix to fix the P-doped, nanoneedle-constructed WO3 flowers. The hierarchically structured P-WO3@TiO2 nanofibrous membrane acts as a self-supported electrocatalyst, presenting an enhanced ammonia yield (6.54 × 10-10 mol s-1 cm-2) and faradaic efficiency (17.5%) compared to the undoped counterpart.

Promoted Electrocatalytic Nitrogen Fixation in Fe-Ni Layered Double Hydroxide Arrays Coupled to Carbon Nanofibers: The Role of Phosphorus Doping.

The key to bringing the electrocatalytic nitrogen fixation from conception to application lies in the development of high-efficiency, cost-effective electrocatalysts. Layered double hydroxides (LDHs), also known as hydrotalcites, are promising electrocatalysts for water splitting due to multiple metal centers and large surface areas. However, their activities in the electrocatalytic nitrogen fixation are unsatisfactory. Now, a simple and effective way of phosphorus doping is presented to regulate the charge distribution in LDHs, thus promoting the nitrogen adsorption and activation. The P-doped LDHs are further coupled to a self-supported, conductive matrix, that is, a carbon nanofibrous membrane, which prevents their aggregation as well as ensuring rapid charge transfer at the interface. By this strategy, decent ammonia yield (1.72×10-10  mol s-1 cm-2 ) and Faradaic efficiency (23 %) are delivered at -0.5 V vs. RHE in 0.1 m Na2 SO4 .

Coordination-Driven Hierarchical Assembly of Hybrid Nanostructures Based on 2D Materials.

2D materials have received tremendous scientific and engineering interests due to their remarkable properties and broad-ranging applications such as energy storage and conversion, catalysis, biomedicine, electronics, and so forth. To further enhance their performance and endow them with new functions, 2D materials are proposed to hybridize with other nanostructured building blocks, resulting in hybrid nanostructures with various morphologies and structures. The properties and functions of these hybrid nanostructures depend strongly on the interfacial interactions between 2D materials and other building blocks. Covalent and coordination bonds are two strong interactions that hold high potential in constructing these robust hybrid nanostructures based on 2D materials. However, most 2D materials are chemically inert, posing problems for the covalent assembly with other building blocks. There are usually coordination atoms in most of 2D materials and their derivatives, thus coordination interaction as a strong interfacial interaction has attracted much attention. In this review, recent progress on the coordination-driven hierarchical assembly based on 2D materials is summarized, focusing on the synthesis approaches, various architectures, and structure-property relationship. Furthermore, insights into the present challenges and future research directions are also presented.