Simultaneously Strengthening and Toughening All-Natural Structural Materials via 3D Nanofiber Network Interfacial Design.

Constructing structural materials from sustainable raw materials is considered an efficient way to reduce the potential threat posed by plastics. Nevertheless, challenges remain regarding combining excellent mechanical and thermal properties, especially the balance of strength and toughness. Here, we report a 3D nanofiber network interfacial design strategy to strengthen and toughen all-natural structural materials simultaneously. The introduced protonated chitosan at the interface between the surface oxidized 3D nanonetwork of bacterial cellulose forms the interfacial interlocking structure of nanonetworks, achieving a robust physical connection and providing enough physical contact sites for chemical crosslinking. The obtained sustainable structural material successfully integrates excellent mechanical and thermal properties on the nanoscale of cellulose nanofibers, such as light weight, high strength, and superior thermal expansion coefficient. The relationship between structural design and comprehensive mechanical property improvement is analyzed in detail, providing a universal perspective to design sustainable high-performance structural materials from nanoscale building blocks.

Functional Carbon Springs Enabled Dynamic Tunable Microwave Absorption and Thermal Insulation.

Electromagnetic (EM) wave pollution and thermal damage pose serious hazards to delicate instruments. Functional aerogels offer a promising solution by mitigating EM interference and isolating heat. However, most of these materials struggle to balance thermal protection with microwave absorption (MA) efficiency due to a previously unidentified conflict between the optimizing strategies of the two properties. Herein, this study reports a solution involving the design of a carbon-based aerogel called functional carbon spring (FCS). Its unique long-range lamellar multi-arch microstructure enables tunable MA performance and excellent thermal insulation capability. Adjusting compression strain from 0% to 50%, the adjustable effective absorption bandwidth (EAB) spans up to 13.4 GHz, covering 84% of the measured frequency spectrum. Notably, at 75% strain, the EAB drops to 0 GHz, demonstrating a novel "on-off" switchability for MA performance. Its ultralow vertical thermal conductivity (12.7 mW m-1 K-1) and unique anisotropic heat transfer mechanism endow FCS with superior thermal protection effectiveness. Numerical simulations demonstrate that FCS outperforms common honeycomb structures and isotropic porous aerogels in thermal management. Furthermore, an "electromagnetic-thermal" dual-protection material database is established, which intuitively demonstrates the superiority of the solution. This work contributes to the advancement of multifunctional MA materials with significant potential for practical applications.

Biomimetic Multimodal Receptors for Comprehensive Artificial Human Somatosensory System.

Electronic skin (e-skin) capable of acquiring environmental and physiological information has attracted interest for healthcare, robotics, and human-machine interaction. However, traditional 2D e-skin only allows for in-plane force sensing, which limits access to comprehensive stimulus feedback due to the lack of out-of-plane signal detection caused by its 3D structure. Here, a dimension-switchable bioinspired receptor is reported to achieve multimodal perception by exploiting film kirigami. It offers the detection of in-plane (pressure and bending) and out-of-plane (force and airflow) signals by dynamically inducing the opening and reclosing of sensing unit. The receptor's hygroscopic and thermoelectric properties enable the sensing of humidity and temperature. Meanwhile, the thermoelectric receptor can differentiate mechanical stimuli from temperature by the voltage. The development enables a wide range of sensory capabilities of traditional e-skin and expands the applications in real life.

Super-Stretchable and High-Energy Micro-Pseudocapacitors Based on MXene Embedded Ag Nanoparticles.

The advancement of aqueous micro-supercapacitors offers an enticing prospect for a broad spectrum of applications, spanning from wearable electronics to micro-robotics and sensors. Unfortunately, conventional micro-supercapacitors are characterized by low capacity and slopy voltage profiles, limiting their energy density capabilities. To enhance the performance of these devices, the use of 2D MXene-based compounds has recently been proposed. Apart from their capacitive contributions, these structures can be loaded with redox-active nanowires which increase their energy density and stabilize their operation voltage. However, introducing rigid nanowires into MXene films typically leads to a significant decline in their mechanical properties, particularly in terms of flexibility. To overcome this issue, super stretchable micro-pseudocapacitor electrodes composed of MXene nanosheets and in situ reconstructed Ag nanoparticles (Ag-NP-MXene) are herein demonstrated, delivering high energy density, stable operation voltage of ≈1 V, and fast charging capabilities. Careful experimental analysis and theoretical simulations of the charging mechanism of the Ag-NP-MXene electrodes reveal a dual nature charge storage mechanism involving ad(de)sorption of ions and conversion reaction of Ag nanoparticles. The superior mechanical properties of synthesized films obtained through in situ construction of Ag-NP-MXene structure show an ultra stretchability, allowing the devices to provide stable voltage and energy output even at 100% elongation.

Hierarchical and reconfigurable interfibrous interface of bioinspired Bouligand structure enabled by moderate orderliness.

Introducing natural Bouligand structure into synthetics is expected to develop high-performance structural materials. Interfibrous interface is critical to load transfer, and mechanical functionality of bioinspired Bouligand structure yet receives little attention. Here, we propose one kind of hierarchical and reconfigurable interfibrous interface based on moderate orderliness to mechanically reinforce bioinspired Bouligand structure. The interface imparted by moderate alignment of adaptable networked nanofibers hierarchically includes nanofiber interlocking and hydrogen-bonding (HB) network bridging, being expected to facilitate load transfer and structural stability through dynamic adjustment in terms of nanofiber sliding and HB breaking-reforming. As one demonstration, the hierarchical and reconfigurable interfibrous interface is constructed based on moderate alignment of networked bacterial cellulose nanofibers. We show that the resultant bioinspired Bouligand structural material exhibits unusual strengthening and toughening mechanisms dominated by interface-microstructure multiscale coupling. The proposed interfibrous interface enabled by moderate orderliness would provide mechanical insight into the assembly of widely existing networked nanofiber building blocks toward high-performance macroscopic bioinspired structural assemblies.

Deformable hard tissue with high fatigue resistance in the hinge of bivalve Cristaria plicata.

The hinge of bivalve shells can sustain hundreds of thousands of repeating opening-and-closing valve motions throughout their lifetime. We studied the hierarchical design of the mineralized tissue in the hinge of the bivalve Cristaria plicata, which endows the tissue with deformability and fatigue resistance and consequently underlies the repeating motion capability. This folding fan-shaped tissue consists of radially aligned, brittle aragonite nanowires embedded in a resilient matrix and can translate external radial loads to circumferential deformation. The hard-soft complex microstructure can suppress stress concentration within the tissue. Coherent nanotwin boundaries along the longitudinal direction of the nanowires increase their resistance to bending fracture. The unusual biomineral, which exploits the inherent properties of each component through multiscale structural design, provides insights into the evolution of antifatigue structural materials.

Artificial Nacre with High Toughness Amplification Factor: Residual Stress-Engineering Sparks Enhanced Extrinsic Toughening Mechanisms.

The high fracture toughness of mollusk nacre is predominantly attributed to the structure-associated extrinsic mechanisms such as platelet sliding and crack deflection. While the nacre-mimetic structures are widely adopted in artificial ceramics, the extrinsic mechanisms are often weakened by the relatively low tensile strength of the platelets with a large aspect ratio, which makes the fracture toughness of these materials much lower than expected. Here, it is demonstrated that the fracture toughness of artificial nacre materials with high inorganic contents can be improved by residual stress-induced platelet strengthening, which can catalyze more effective extrinsic toughening mechanisms that are specific to the nacre-mimetic structures. Thereby, while the absolute fracture toughness of the materials is not comparable with advanced ceramic-based composites, the toughness amplification factor of the material reaches 16.1 ± 1.1, outperforming the state-of-the-art biomimetic ceramics. The results reveal that, with the merit of nacre-mimetic structural designs, the overall fracture toughness of the artificial nacre can be improved by the platelet strengthening through extrinsic toughening mechanisms, although the intrinsic fracture toughness may decrease at platelet level due to the strengthening. It is anticipated that advanced structural ceramics with exceeding performance can be fabricated through these unconventional strategies.

A Highly Compressible and Stretchable Carbon Spring for Smart Vibration and Magnetism Sensors.

Porous carbon materials demonstrate extensive applications for their attractive characteristics. Mechanical flexibility is an essential property guaranteeing their durability. After decades of research efforts, compressive brittleness of porous carbon materials is well resolved. However, reversible stretchability remains challenging to achieve due to the intrinsically weak connections and fragile joints of the porous carbon networks. Herein, it is presented that a porous all-carbon material achieving both elastic compressibility and stretchability at large strain from -80% to 80% can be obtained when a unique long-range lamellar multi-arch microstructure is introduced. Impressively, the porous all-carbon material can maintain reliable structural robustness and durability under loading condition of cyclic compressing-stretching process, similar to a real metallic spring. The unique performance renders it as a promising platform for making smart vibration and magnetism sensors, even capable of operating at extreme temperatures. Furthermore, this study provides valuable insights for creating highly stretchable and compressible porous materials from other neat inorganic components for diverse applications in future.

Bioinspired hierarchical helical nanocomposite macrofibers based on bacterial cellulose nanofibers.

Bio-sourced nanocellulosic materials are promising candidates for spinning high-performance sustainable macrofibers for advanced applications. Various strategies have been pursued to gain nanocellulose-based macrofibers with improved strength. However, nearly all of them have been achieved at the expense of their elongation and toughness. Inspired by the widely existed hierarchical helical and nanocomposite structural features in biosynthesized fibers exhibiting exceptional combinations of strength and toughness, we report a design strategy to make nanocellulose-based macrofibers with similar characteristics. By combining a facile wet-spinning process with a subsequent multiple wet-twisting procedure, we successfully obtain biomimetic hierarchical helical nanocomposite macrofibers based on bacterial cellulose nanofibers, realizing impressive improvement in their tensile strength, elongation and toughness simultaneously. The achievement certifies the validity of the bioinspired hierarchical helical and nanocomposite structural design proposed here. This bioinspired design strategy provides a potential platform for further optimizing or creating many more strong and tough nanocomposite fiber materials for diverse applications.

Unidirectional and Selective Proton Transport in Artificial Heterostructured Nanochannels with Nano-to-Subnano Confined Water Clusters.

The construction of biological proton channel analogues has attracted substantial interest owing to their wide potential in separation of ions, sensing, and energy conversion. Here, metal-organic framework (MOF)/polymer heterogeneous nanochannels are presented, in which water molecules are confined to disordered clusters in the nanometer-sized polymer regions and to ordered chains with unique molecular configurations in the 1D sub-1-nm porous MOF regions, to realize unidirectional, fast, and selective proton transport properties, analogous to natural proton channels. Given the nano-to-subnano confined water junctions, experimental proton conductivities in the polymer-to-MOF direction of the channels are much higher than those in the opposite direction, showing a high rectification up to 500 and one to two orders of magnitude enhancement compared to the conductivity of proton transport in bulk water. The channels also show a good proton selectivity over other cations. Theoretical simulations further reveal that the preferential and fast proton conduction in the nano-to-subnano channel direction is attributed to extremely low energy barriers for proton transport from disordered to ordered water clusters. This study opens a novel approach to regulate ion permeability and selectivity of artificial ion channels.

Lightweight, tough, and sustainable cellulose nanofiber-derived bulk structural materials with low thermal expansion coefficient.

Sustainable structural materials with light weight, great thermal dimensional stability, and superb mechanical properties are vitally important for engineering application, but the intrinsic conflict among some material properties (e.g., strength and toughness) makes it challenging to realize these performance indexes at the same time under wide service conditions. Here, we report a robust and feasible strategy to process cellulose nanofiber (CNF) into a high-performance sustainable bulk structural material with low density, excellent strength and toughness, and great thermal dimensional stability. The obtained cellulose nanofiber plate (CNFP) has high specific strength [~198 MPa/(Mg m-3)], high specific impact toughness [~67 kJ m-2/(Mg m-3)], and low thermal expansion coefficient (<5 × 10-6 K-1), which shows distinct and superior properties to typical polymers, metals, and ceramics, making it a low-cost, high-performance, and environmental-friendly alternative for engineering requirement, especially for aerospace applications.

Superelastic Hard Carbon Nanofiber Aerogels.

Superelastic carbon aerogels have been widely explored by graphitic carbons and soft carbons. These soft aerogels usually have delicate microstructures with good fatigue resistance but ultralow strength. Hard carbon aerogels show great advantages in mechanical strength and structural stability due to the sp3 -C-induced turbostratic "house-of-cards" structure. However, it is still a challenge to fabricate superelastic hard carbon-based aerogels. Through rational nanofibrous structural design, the traditional rigid phenolic resin can be converted into superelastic hard carbon aerogels. The hard carbon nanofibers and abundant welded junctions endow the hard carbon aerogels with robust and stable mechanical performance, including superelasticity, high strength, extremely fast recovery speed (860 mm s-1 ), low energy-loss coefficient (<0.16), long cycle lifespan, and heat/cold-endurance. These emerging hard carbon nanofiber aerogels hold a great promise in the application of piezoresistive stress sensors with high stability and wide detection range (50 kPa), as well as stretchable or bendable conductors.

Modulation of Molecular Spatial Distribution and Chemisorption with Perforated Nanosheets for Ethanol Electro-oxidation.

Integrating thermodynamically favorable ethanol reforming reactions with hybrid water electrolysis will allow room-temperature production of high-value organic products and decoupled hydrogen evolution. However, electrochemical reforming of ethanol has not received adequate attention due to its low catalytic efficiency and poor selectivity, which are caused by the multiple groups and chemical bonds of ethanol. In addition to the thermodynamic properties affected by the electronic structure of the catalyst, the dynamics of molecule/ion dynamics in electrolytes also play a significant role in the efficiency of a catalyst. The relatively large size and viscosity of the ethanol molecule necessitates large channels for molecule/ion transport through catalysts. Perforated CoNi hydroxide nanosheets are proposed as a model catalyst to synergistically regulate the dynamics of molecules and electronic structures. Molecular dynamics simulations directly reveal that these nanosheets can act as a "dam" to enrich ethanol molecules and facilitate permeation through the nanopores. Additionally, the charge transfer behavior of heteroatoms modifies the local charge density to promote molecular chemisorption. As expected, the perforated nanosheets exhibit a small potential (1.39 V) and high Faradaic efficiency for the conversion of ethanol into acetic acid. Moreover, the concept in this work provides new perspectives for exploring other molecular catalysts.

Molecular mechanism of viscoelastic polymer enhanced oil recovery in nanopores.

Polymer flooding is a promising chemical enhanced oil recovery (EOR) method, which realizes more efficient extraction in porous formations characterized with nanoscale porosity and complicated interfaces. Understanding the molecular mechanism of viscoelastic polymer EOR in nanopores is of great significance for the advancement of oil exploitation. Using molecular dynamics simulations, we investigated the detailed process of a viscoelastic polymer displacing oil at the atomic scale. We found that the interactions between polymer chains and oil provide an additional pulling effect on extracting the residual oil trapped in dead-end nanopores, which plays a key role in increasing the oil displacement efficiency. Our results also demonstrate that the oil displacement ability of polymer can be reinforced with the increasing chain length and viscoelasticity. In particular, a polymer with longer chain length exhibits stronger elastic property, which enhances the foregoing pulling effect. These findings can help to enrich our understanding on the molecular mechanism of polymer enhanced oil recovery and provide guidance for oil extraction engineering.

Bioinspired polymeric woods.

Woods provide bioinspiration for engineering materials due to their superior mechanical performance. We demonstrate a novel strategy for large-scale fabrication of a family of bioinspired polymeric woods with similar polyphenol matrix materials, wood-like cellular microstructures, and outstanding comprehensive performance by a self-assembly and thermocuring process of traditional resins. In contrast to natural woods, polymeric woods demonstrate comparable mechanical properties (a compressive yield strength of up to 45 MPa), preferable corrosion resistance to acid with no decrease in mechanical properties, and much better thermal insulation (as low as ~21 mW m-1 K-1) and fire retardancy. These bioinspired polymeric woods even stand out from other engineering materials such as cellular ceramic materials and aerogel-like materials in terms of specific strength and thermal insulation properties. The present strategy provides a new possibility for mass production of a series of high-performance biomimetic engineering materials with hierarchical cellular microstructures and remarkable multifunctionality.

Joule-heated graphene-wrapped sponge enables fast clean-up of viscous crude-oil spill.

The clean-up of viscous crude-oil spills is a global challenge. Hydrophobic and oleophilic oil sorbents have been demonstrated as promising candidates for oil-spill remediation. However, the sorption speeds of these oil sorbents for viscous crude oil are rather limited. Herein we report a Joule-heated graphene-wrapped sponge (GWS) to clean-up viscous crude oil at a high sorption speed. The Joule heat of the GWS reduced in situ the viscosity of the crude oil, which prominently increased the oil-diffusion coefficient in the pores of the GWS and thus speeded up the oil-sorption rate. The oil-sorption time was reduced by 94.6% compared with that of non-heated GWS. Besides, the oil-recovery speed was increased because of the viscosity decrease of crude oil. This in situ Joule self-heated sorbent design will promote the practical application of hydrophobic and oleophilic oil sorbents in the clean-up of viscous crude-oil spills.

Super-elastic and fatigue resistant carbon material with lamellar multi-arch microstructure.

Low-density compressible materials enable various applications but are often hindered by structure-derived fatigue failure, weak elasticity with slow recovery speed and large energy dissipation. Here we demonstrate a carbon material with microstructure-derived super-elasticity and high fatigue resistance achieved by designing a hierarchical lamellar architecture composed of thousands of microscale arches that serve as elastic units. The obtained monolithic carbon material can rebound a steel ball in spring-like fashion with fast recovery speed (∼580 mm s-1), and demonstrates complete recovery and small energy dissipation (∼0.2) in each compress-release cycle, even under 90% strain. Particularly, the material can maintain structural integrity after more than 106 cycles at 20% strain and 2.5 × 105 cycles at 50% strain. This structural material, although constructed using an intrinsically brittle carbon constituent, is simultaneously super-elastic, highly compressible and fatigue resistant to a degree even greater than that of previously reported compressible foams mainly made from more robust constituents.