Improving strength and toughness of graphene film through metal ion bridging.

The fangs, jaws, and mandibles of marine invertebrates such as Chiton and Glycera show excellent mechanical properties, which are mostly contributed to the interactions between metal (Fe, Cu, Zn, etc.) and oxygen-containing functional groups in proteins. Inspired by these load-bearing skeletal biomaterials, we improved tensile strength and toughness of graphene films through bridging graphene oxide (GO) nanosheets by metal ions. By optimizing the metal coordination form and density of cross-linking network. We revealed the relationship between mechanical properties and the unique spatial geometry of the GO nanosheets bridged by different valence metal ions. The results demonstrated that the divalent metal ions form tetrahedral geometry with carboxylate groups on the edges of the GO nanosheets, and the bond energy is relatively low, which is helpful for improving the toughness of resultant graphene films. While the trivalent metal ions are easily to form octahedral geometry with the GO nanosheets with higher bond energy, which is better for enhancing the tensile strength of graphene films. After reduction, the reduced GO (rGO) film bridged by divalent metal ions shows 43% improvement in toughness, while the rGO film bridged by trivalent metal ions shows 64% improvement in tensile strength. Our work reveals the mechanism of metal coordination bond energy and spatial geometry to improve the mechanical properties of graphene films, which lays a theoretical foundation for improving the tensile strength and toughness of resultant graphene films, and provides an avenue for fabricating high-performance graphene films and other two-dimensional nanocomposites.

Ginkgo seed shell provides a unique model for bioinspired design.

Natural structural materials typically feature complex hierarchical anisotropic architectures, resulting in excellent damage tolerance. Such highly anisotropic structures, however, also provide an easy path for crack propagation, often leading to catastrophic fracture as evidenced, for example, by wood splitting. Here, we describe the weakly anisotropic structure of Ginkgo biloba (ginkgo) seed shell, which has excellent crack resistance in different directions. Ginkgo seed shell is composed of tightly packed polygonal sclereids with cell walls in which the cellulose microfibrils are oriented in a helicoidal pattern. We found that the sclereids contain distinct pits, special fine tubes like a "screw fastener," that interlock the helicoidal cell walls together. As a result, ginkgo seed shell demonstrates crack resistance in all directions, exhibiting specific fracture toughness that can rival other highly anisotropic natural materials, such as wood, bone, insect cuticle, and nacre. In situ characterization reveals ginkgo's unique toughening mechanism: pit-guided crack propagation. This mechanism forces the crack to depart from the weak compound middle lamella and enter into the sclereid, where the helicoidal cell wall significantly inhibits crack growth by the cleavage and breakage of the fibril-based cell walls. Ginkgo's toughening mechanism could provide guidelines for a new bioinspired strategy for the design of high-performance bulk materials.

Strong and Tough MXene Bridging-induced Conductive Nacre.

Nacre is a classic model, providing an inspiration for fabricating high-performance bulk nanocomposites with the two-dimensional platelets. However, the "brick" of nacre, aragonite platelet, is an ideal building block for making high-performance bulk nanocomposites. Herein, we demonstrated a strong and tough conductive nacre through reassembling aragonite platelets with bridged by MXene nanosheets and hydrogen bonding, not only providing high mechanical properties but also excellent electrical conductivity. The flexural strength and fracture toughness of the obtained conductive nacre reach ~282 MPa and ~6.3 MPa m1/2, which is 1.6 and 1.6 times higher than that of natural nacre, respectively. These properties are attributed to densification and high orientation degree of the conductive nacre, which is effectively induced by the combined interactions of hydrogen bonding and MXene nanosheets bridging. The crack propagations in conductive nacre are effectively inhibited through crack deflection with hydrogen bonding, and MXene nanosheets bridging between aragonite platelets. In addition, our conductive nacre also provides a self-monitoring function for structural damage and offers exceptional electromagnetic interference shielding performance. Our strategy of reassembling the aragonite platelets exfoliated from waste nacre into high-performance artificial nacre, provides an avenue for fabricating high-performance bulk nanocomposites through the sustainable reutilization of shell resources.

Strong sequentially bridged MXene sheets.

Titanium carbide (Ti3C2Tx) MXene has great potential for use in aerospace and flexible electronics due to its excellent electrical conductivity and mechanical properties. However, the assembly of MXene nanosheets into macroscopic high-performance nanocomposites is challenging, limiting MXene's practical applications. Here we describe our work fabricating strong and highly conductive MXene sheets through sequential bridging of hydrogen and ionic bonding. The ionic bonding agent decreases interplanar spacing and increases MXene nanosheet alignment, while the hydrogen bonding agent increases interplanar spacing and decreases MXene nanosheet alignment. Successive application of hydrogen and ionic bonding agents optimizes toughness, tensile strength, oxidation resistance in a humid environment, and resistance to sonication disintegration and mechanical abuse. The tensile strength of these MXene sheets reaches up to 436 MPa. The electrical conductivity and weight-normalized shielding efficiency are also as high as 2,988 S/cm and 58,929 dB∙cm2/g, respectively. The toughening and strengthening mechanisms are revealed by molecular-dynamics simulations. Our sequential bridging strategy opens an avenue for the assembly of other high-performance MXene nanocomposites.

Ultratough graphene-black phosphorus films.

Graphene-based films with high toughness have many promising applications, especially for flexible energy storage and portable electrical devices. Achieving such high-toughness films, however, remains a challenge. The conventional mechanisms for improving toughness are crack arrest or plastic deformation. Herein we demonstrate black phosphorus (BP) functionalized graphene films with record toughness by combining crack arrest and plastic deformation. The formation of covalent bonding P-O-C between BP and graphene oxide (GO) nanosheets not only reduces the voids of GO film but also improves the alignment degree of GO nanosheets, resulting in high compactness of the GO film. After further chemical reduction and π-π stacking interactions by conjugated molecules, the alignment degree of rGO nanosheets was further improved, and the voids in lamellar graphene film were also further reduced. Then, the compactness of the resultant graphene films and the alignment degree of reduced graphene oxide nanosheets are further improved. The toughness of the graphene film reaches as high as ∼51.8 MJ m-3, the highest recorded to date. In situ Raman spectra and molecular dynamics simulations reveal that the record toughness is due to synergistic interactions of lubrication of BP nanosheets, P-O-C covalent bonding, and π-π stacking interactions in the resultant graphene films. Our tough black phosphorus functionalized graphene films with high tensile strength and excellent conductivity also exhibit high ambient stability and electromagnetic shielding performance. Furthermore, a supercapacitor based on the tough films demonstrated high performance and remarkable flexibility.

Tough and Conductive Nacre-inspired MXene/Epoxy Layered Bulk Nanocomposites.

A long-standing quest in materials science has been the development of tough epoxy resin nanocomposites for use in numerous applications. Inspired by nacre, here we report tough and conductive MXene/epoxy layered bulk nanocomposites. The orientation of MXene lamellar scaffolds is enhanced by annealing treatment. The improved interfacial interactions between MXene lamellar scaffold and epoxy through surface chemical modification resulted in a synergistic effect. Tailoring the interlayer spacing of MXene nanosheets to a critical distance resulted in a fracture toughness about eight times higher than that of pure epoxy, surpassing other epoxy nanocomposites. Our nacre-inspired MXene/epoxy layered bulk nanocomposites also show high electrical conductivity that provides self-monitoring capability for structural integrity and exhibits an excellent electromagnetic interference shielding efficiency. Our proposed strategy provides an avenue for fabricating high-performance epoxy nanocomposites.

High-strength scalable graphene sheets by freezing stretch-induced alignment.

ABSTRACCT: Efforts to obtain high-strength graphene sheets by near-room-temperature assembly have been frustrated by the misalignment of graphene layers, which degrades mechanical properties. While in-plane stretching can decrease this misalignment, it reappears when releasing the stretch. Here we use covalent and π-π inter-platelet bridging to permanently freeze stretch-induced alignment of graphene sheets, and thereby increase isotropic in-plane sheet strength to 1.55 GPa, in combination with a high Young's modulus, electrical conductivity and weight-normalized shielding efficiency. Moreover, the stretch-bridged graphene sheets are scalable and can be easily bonded together using a commercial resin without appreciably decreasing the performance, which establishes the potential for practical applications.

MXene-Regulated Perovskite Vertical Growth for High-Performance Solar Cells.

Defects at the interfaces of perovskite (PVK) thin films are the main factors responsible for instability and low photoelectric conversion efficiency (PCE) of PVK solar cells (PSCs). Here, a SnO2 -MXene composite electron transport layer (ETL) is used in PSCs to improve interfacial contact and passivate defects at the SnO2 /perovskite interface. The introduced MXene regulates SnO2 dispersion and induces a vertical growth of PVK. The lattice matching of MXene and perovskite suppresses the concentration of interfacial stress, thereby obtaining a perovskite film with low defects. Compared with SnO2 -based device, the PCE of SnO2 -MXene-based device is improved by 15 % and its short-circuit current is up to 25.07 mA cm-2 . Furthermore, unencapsulated device maintained about 90 % of its initial efficiency even after 500 h of storage at 30-40 % relative humidity in ambient air. The composite ETL strategy provides a route to engineer interfacial passivation between metal halide perovskites and ETLs.

Moiré-Potential-Induced Band Structure Engineering in Graphene and Silicene.

A moiré pattern results from the projection of one periodic pattern to another with relative lattice constant or misalignment and provides great periodic potential to modify the electronic properties of pristine materials. In this Review, recent research on the effect of the moiré superlattice on the electronic structures of graphene and silicene, both of which possess a honeycomb lattice, is focused on. The moiré periodic potential is introduced by the interlayer interaction to realize abundant phenomena, including new generation of Dirac cones, emergence of Van Hove singularities (vHs) at the cross point of two sets of Dirac cones, Mott-like insulating behavior at half-filling state, unconventional superconductivity, and electronic Kagome lattice and flat band with nontrivial edge state. The role of interlayer coupling strength, which is determined by twist angle and buckling degree, in these exotic properties is discussed in terms of both the theoretical prediction and experimental measurement, and finally, the challenges and outlook for this field are discussed.

Near-Infrared-Driven Photocatalysts: Design, Construction, and Applications.

Photocatalysts, which utilize solar energy to catalyze the oxidation or reduction half reactions, have attracted tremendous interest due to their great potential in addressing increasingly severe global energy and environmental issues. Solar energy utilization plays an important role in determining photocatalytic efficiencies. In the past few decades, many studies have been done to promote photocatalytic efficiencies via extending the absorption of solar energy into near-infrared (NIR) light. This Review comprehensively summarizes the recent progress in NIR-driven photocatalysts, including the strategies to harvest NIR photons and corresponding photocatalytic applications such as the degradation of organic pollutants, water disinfection, water splitting for H2 and O2 evolution, CO2 reduction, etc. The application of NIR-active photocatalysts employed as electrocatalysts is also presented. The subject matter of this Review is designed to present the relationship between material structure and material optical properties as well as the advantage of material modification in photocatalytic reactions. It paves the way for future material design in solar energy-related fields and other energy conversion and storage fields.

Sequentially bridged graphene sheets with high strength, toughness, and electrical conductivity.

We here show that infiltrated bridging agents can convert inexpensively fabricated graphene platelet sheets into high-performance materials, thereby avoiding the need for a polymer matrix. Two types of bridging agents were investigated for interconnecting graphene sheets, which attach to sheets by either π-π bonding or covalent bonding. When applied alone, the π-π bonding agent is most effective. However, successive application of the optimized ratio of π-π bonding and covalent bonding agents provides graphene sheets with the highest strength, toughness, fatigue resistance, electrical conductivity, electromagnetic interference shielding efficiency, and resistance to ultrasonic dissolution. Raman spectroscopy measurements of stress transfer to graphene platelets allow us to decipher the mechanisms of property improvement. In addition, the degree of orientation of graphene platelets increases with increasing effectiveness of the bonding agents, and the interlayer spacing increases. Compared with other materials that are strong in all directions within a sheet, the realized tensile strength (945 MPa) of the resin-free graphene platelet sheets was higher than for carbon nanotube or graphene platelet composites, and comparable to that of commercially available carbon fiber composites. The toughness of these composites, containing the combination of π-π bonding and covalent bonding, was much higher than for these other materials having high strengths for all in-plane directions, thereby opening the path to materials design of layered nanocomposites using multiple types of quantitatively engineered chemical bonds between nanoscale building blocks.

Chemical Strategies for Making Strong Graphene Materials.

Graphene materials have been widely applied in various fields because of their remarkable mechanical and electrical properties. However, two obstacles arise during the assembly of graphene platelets into macroscale graphene materials and composites that impair the performance of the resultant graphene materials: 1) the voids between the graphene platelets, and 2) the wrinkling of the graphene platelets. In the past decade, several strategies have been developed to eliminate these obstacles. These strategies result in strong macroscale graphene materials, such as graphene fibers with tensile strengths of over 3.4 GPa and sheets with tensile strengths of over 1.5 GPa, which have many practical applications. This Minireview summarizes the effective strategies for assembling graphene materials and compares their advantages and drawbacks. The preparation processes as well as the resulting fundamental mechanical properties and wide spectrum of electrical and magnetic properties are also discussed. Finally, our outlook for the future of this field is presented.

Bioinspired Color Switchable Photonic Crystal Silicone Elastomer Kirigami.

Bioinspired dynamic structural color has great potential for use in dynamic displays, sensors, cryptography, and camouflage. However, it is quite rare for artificial structural color devices to withstand thousands of cycles. Male hummingbird's crowns and gorgets are brightly colored, demonstrating frequent color switching that is induced by regulating the orientation of the feathers through movement of skin or joints. Inspired by this unique structural color modulation, we demonstrate a flexible, mechanically triggered color switchable sheet based on a photonic crystal (PhC)-coated polydimethylsiloxane (PDMS) kirigami (PhC-PDMS kirigami) made by laser cutting. Finite element modeling (FEM) simulation reveals that the thickness of PDMS kirigami and the chamfer at the incision induced by laser cutting both dominate the out-of-plane deformation through in-plane stretching. The bioinspired PhC-PDMS kirigami shows precisely programmable structural color and keeps the color very well after recycling over 10 000 times. This bioinspired PhC-PDMS kirigami also shows excellent viewability even in bright sunlight, high readability, robust functionality, technical flexibility, and mechanical durability, which are readily exploitable for applications, such as chromic mechanical monitors for the sports industry or for medical applications, wearable camouflage, and security systems.

Ultra-Tough Inverse Artificial Nacre Based on Epoxy-Graphene by Freeze-Casting.

Epoxy nanocomposites combining high toughness with advantageous functional properties are needed in many fields. However, fabricating high-performance homogeneous epoxy nanocomposites with traditional methods remains a great challenge. Nacre with outstanding fracture toughness presents an ideal blueprint for the development of future epoxy nanocomposites. Now, high-performance epoxy-graphene layered nanocomposites were demonstrated with ultrahigh toughness and temperature-sensing properties. These nanocomposites are composed of ca. 99 wt % organic epoxy, which is in contrast to the composition of natural nacre (ca. 96 wt % inorganic aragonite). These nanocomposites are named an inverse artificial nacre. The fracture toughness reaches about 4.2 times higher than that of pure epoxy. The electrical resistance is temperature-sensitive and stable under various humidity conditions. This strategy opens an avenue for fabricating high-performance epoxy nanocomposites with functional properties.

A Butterfly-Inspired Hierarchical Light-Trapping Structure towards a High-Performance Polarization-Sensitive Perovskite Photodetector.

Extensive applications for photodetectors have led to demand for high-responsivity polarization-sensitive light detection. Inspired by the elaborate architecture of butterfly Papilio paris, a 1D nanograting bonded porous 2D photonic crystal perovskite photodetector (G-PC-PD) using a commercial DVD master and 2D crystalline colloidal arrays template was fabricated. The coupling effect from grating diffraction and reflection of the PC stopband renders the enhanced light harvesting of G-PC-PD. The porous scaffold and nanoimprinting process afford a highly crystalline perovskite film. White light responsivity and detectivity of G-PC-PD are up to 12.67 A W-1 and 3.22×1013  Jones (6∼7 times that of a pristine perovskite photodetector). The highly ordered nanograting arrays of G-PC-PD enable polarization-sensitive light detection with a rate of -0.72 nA deg-1 . This hierarchical perovskite integrated nanograting and 2D PC architecture opens a new avenue to high-performance optoelectronic devices.

Smart Nacre-inspired Nanocomposites.

Nacre-inspired nanocomposites with excellent mechanical properties have achieved remarkable attention in the past decades. The high performance of nacre-inspired nanocomposites is a good basis for the further application of smart devices. Recently, some smart nanocomposites inspired by nacre have demonstrated good mechanical properties as well as effective and stable stimuli-responsive functions. In this Concept, we summarize the recent development of smart nacre-inspired nanocomposites, including 1D fibers, 2D films and 3D bulk nanocomposites, in response to temperature, moisture, light, strain, and so on. We show that diverse smart nanocomposites could be designed by combining various conventional fabrication methods of nacre-inspired nanocomposites with responsive building blocks and interface interactions. The nacre-inspired strategy is versatile for different kinds of smart nanocomposites in extensive applications, such as strain sensors, displays, artificial muscles, robotics, and so on, and may act as an effective roadmap for designing smart nanocomposites in the future.

Graphene-based artificial nacre nanocomposites.

With its extraordinary properties as the strongest and stiffest material ever measured and the best-known electrical conductor, graphene could have promising applications in many fields, especially in the area of nanocomposites. However, processing graphene-based nanocomposites is very difficult. So far, graphene-based nanocomposites exhibit rather poor properties. Nacre, the gold standard for biomimicry, provides an excellent example and guidelines for assembling two-dimensional nanosheets into high performance nanocomposites. The inspiration from nacre overcomes the bottleneck of traditional approaches for constructing nanocomposites, such as poor dispersion, low loading, and weak interface interactions. This tutorial review summarizes recent research on graphene-based artificial nacre nanocomposites and focuses on the design of interface interactions and synergistic effects for constructing high performance nanocomposites. This tutorial review also focuses on a perspective of the dynamic area of graphene-based nanocomposites, commenting on whether the concept is viable and practical, on what has been achieved to date, and most importantly, what is likely to be achieved in the future.

Mimicking Nacre by Ice Templating.

Ice-T loves nacre: An ice-templating approach resulted in a series of high-performance lamellar composites. This novel bioinspired approach opens up new opportunities for the preparation of bulk composite materials with tunable nano- and microscopic structures and various constituents.

Bioinspired layered materials with superior mechanical performance.

Nature has inspired researchers to construct structures with ordered layers as candidates for new materials with high mechanical performance. As a prominent example, nacre, also known as mother of pearl, consists of a combination of inorganic plates (aragonite calcium carbonate, 95% by volume) and organic macromolecules (elastic biopolymer, 5% by volume) and shows a unique combination of strength and toughness. Investigations of its structure reveal that the hexagonal platelets of calcium carbonate and the amorphous biopolymer are alternatively assembled into the orderly layered structure. The delicate interface between the calcium carbonate and the biopolymer is well defined. Both the building blocks that make up these assembled layers and the interfaces between the inorganic and organic components contribute to the excellent mechanical property of natural nacre. In this Account, we summarize recent research from our group and from others on the design of bioinspired materials composed by layering various primitive materials. We focus particular attention on nanoscale carbon materials. Using several examples, we describe how the use of different combinations of layered materials leads to particular properties. Flattened double-walled carbon nanotubes (FDWCNTs) covalently cross-linked in a thermoset three-dimensional (3D) network produced the materials with the highest strength. The stiffest layered materials were generated from borate orthoester covalent bonding between adjacent graphene oxide (GO) nanosheets, and the toughest layered materials were fabricated with Al2O3 platelets and chitosan via hydrogen bonding. These new building blocks, such as FDWCNTs and GO, and the replication of the elaborate micro-/nanoscale interface of natural nacre have provided many options for developing new high performance artificial materials. The interface designs for bioinspired layered materials are generally categorized into (1) hydrogen bonding, (2) ionic bonding, and (3) covalent bonding. Using these different strategies, we can tune the materials to have specific mechanical characteristics such as high strength, excellent strain resistance, or remarkable toughness. Among these design strategies, hydrogen bonding affords soft interfaces between the inorganic plates and the organic matrix. Covalent cross-linking forms chemical bonds between the inorganic plates and the organic matrix, leading to much stronger interfaces. The interfaces formed by ionic bonding are stronger than those formed by hydrogen bonding but weaker than those formed by covalent bonding.

Bioinspired green composite lotus fibers.

Owing to the growing global environmental problems, demands for environmentally friendly, fully biodegradable sustainable composites have substantially increased across various industries. Inspired by the composite structure of cocoon silk, we fabricated a fully green composite fiber (GCF) that is based on the lotus fiber (LF) and a biodegradable polymer, namely poly(vinyl alcohol) (PVA). After the formation of cross-linkages between the LF and PVA, the mechanical properties of this bioinspired GCF had substantially improved. In particular, the specific mechanical properties are superior to those of cocoon silk and other natural fibers. These findings suggest that LFs may be used as reinforcement materials for the fabrication of bulk green materials for various industries, such as the textile, medical, automobile, and aerospace industries.