Designing Ultratough Single-Network Hydrogels with Centimeter-Scale Fractocohesive Lengths via Inelastic Crack Blunting.

Fractocohesive length, defined as the ratio of fracture toughness to work of fracture, measures the sensitivity of materials to fracture in the presence of flaws. The larger the fractocohesive length, the more flaw-tolerant and crack-resistant the hydrogel. For synthetic soft materials, the fractocohesive length is short, often on the scale of 1 mm. Here, highly flaw-insensitive (HFI) single-network hydrogels containing an entangled inhomogeneous polymer network of widely distributed chain lengths are designed. The HFI hydrogels demonstrate a centimeter-scale fractocohesive length of 2.21 cm, which is the highest ever recorded for synthetic hydrogels, and an unprecedented fracture toughness of ≈13 300 J m-2 . The uncommon flaw insensitivity results from the inelastic crack blunting inherent to the highly inhomogeneous network. When the HFI hydrogel is stretched, a large number of short chains break while coiled long chains can disentangle, unwind, and straighten, producing large inelastic deformation that substantially blunts the crack tip in a plastic manner, thereby deconcentrating crack-tip stresses and blocking crack extension. The flaw-insensitive design strategy is applicable to various hydrogels such as polyacrylamide and poly(N,N-dimethylacrylamide) hydrogels and enables the development of HFI soft composites.

Extreme Environmental Thermal Shock Induced Dislocation-Rich Pt Nanoparticles Boosting Hydrogen Evolution Reaction.

Crystal structure engineering of nanomaterials is crucial for the design of electrocatalysts. Inducing dislocations is an efficient approach to generate strain effects in nanomaterials to optimize the crystal and electronic structures and improve the catalytic properties. However, it is almost impossible to produce and retain dislocations in commercial mainstream catalysts, such as single metal platinum (Pt) catalysts. In this work, a non-equilibrium high-temperature (>1400 K) thermal-shock method is reported to induce rich dislocations in Pt nanocrystals (Dr-Pt). The method is performed in an extreme environment (≈77 K) created by liquid nitrogen. The dislocations induced within milliseconds by thermal and structural stress during the crystallization process are kinetically frozen at an ultrafast cooling rate. The high-energy surface structures with dislocation-induced strain effects can prevent surface restructuring during catalysis. The findings indicate that a novel extreme environmental high-temperature thermal-shock method can successfully introduce rich dislocations in Pt nanoparticles and significantly boost its hydrogen evolution reaction performance.

Mechanics Design in Cellulose-Enabled High-Performance Functional Materials.

The abundance of cellulose found in natural resources such as wood, and the wide spectrum of structural diversity of cellulose nanomaterials in the form of micro-nano-sized particles and fibers, have sparked a tremendous interest to utilize cellulose's intriguing mechanical properties in designing high-performance functional materials, where cellulose's structure-mechanics relationships are pivotal. In this progress report, multiscale mechanics understanding of cellulose, including the key role of hydrogen bonding, the dependence of structural interfaces on the spatial hydrogen bond density, the effect of nanofiber size and orientation on the fracture toughness, are discussed along with recent development on enabling experimental design techniques such as structural alteration, manipulation of anisotropy, interface and topology engineering. Progress in these fronts renders cellulose a prospect of being effectuated in an array of emerging sustainable applications and being fabricated into high-performance structural materials that are both strong and tough.

Controlling Rotation of Two-Dimensional Material Flakes.

Interlayer rotational alignment in van der Waals (vdW) structures of two-dimensional (2D) materials couples strongly to electronic properties and, therefore, has significant technological implications. Nevertheless, controlling the rotation of an arbitrary 2D material flake remains a challenge in the development of rotation-tunable electronics, for the emerging field of twistronics. In this article, we reveal a general moiré-driven mechanism that governs the interlayer rotation. Controlling the moiré can therefore hold promise for controlling the interlayer rotation. We further demonstrate mismatch strain engineering as a useful tool to design the interlayer rotation via changing the energy landscape of moiré within a finite-sized region. The robustness and programmable nature of our approach arise from moiré symmetry, energetics, and mechanics. Our approach provides another possibility to the on-demand design of rotation-tunable electronics.

One-Step, Catalyst-Free, Scalable in Situ Synthesis of Single-Crystal Aluminum Nanowires in Confined Graphene Space.

Nanowires have a wide range of applications, such as transparent electrodes, Li-ion battery anodes, light-emitting diodes, solar cells, and electronic devices. Currently, aluminum (Al) nanowires can be synthesized by thermally induced substitution of germanium (Ge) nanowires, chemical vapor deposition on other metal substrates, and template-assisted growth methods. However, there are still challenges in fabricating extremely high-purity nanowires, large-scale manufacturing, and simplifying the synthesis process and conditions. Here, we report for the first time that single-crystal Al nanowires can be one-step, in situ synthesized on a reduced graphene oxide (RGO) substrate on a large scale without using any catalysts. Through a simple high temperature treatment process, commercial micro-sized Al powders in RGO film were transformed into a single-crystal Al nanowire with an average length of 1.2 µm and an average diameter of 18 nm. The possible formation mechanism of the single-crystal Al nanowires is proposed as follows: hot aluminum atoms eject from the pristine aluminum/alumina core/shell structure of Al powders when they build up enough energy from the thermal stress under high temperature and confined space conditions, which is supported by both experimental and computational results. The method introduced here can be extended to allow the synthesis of one-dimensional highly reactive materials, like alkali metal nanowires, in confined spaces.

Moiré-templated strain patterning in transition-metal dichalcogenides and application in twisted bilayer MoS2.

To take full advantage of the electronic properties of transition-metal dichalcogenides and their vdW layered structures, it will be necessary to control the local electronic structure, on which the effect of lattice deformation is significant. Nevertheless, a general approach to programming nanoscale morphology in TMD materials, which would permit local strain engineering, has proven elusive. In this work, we propose a general moiré-templated nanoscale morphology engineering method based on bilayer TMDs. The moiré superlattice plays the key role in enforcing in-plane periodical variations in local interlayer spacing and potential energy. Upon global in-plane compression, the high-energy, large-interlayer-separation stacking domains serve as periodic buckling initiation sites. The buckled features can be thus precisely correlated to the moiré periodicity. The spatial profile of the buckled morphology and strain field are possible to be pre-determined, providing a bridge to the electronics and optoelectronics design. We take twisted bilayer MoS2 to demonstrate our approach. We further demonstrate how the morphology can modulate band gap and optical absorption of a MoS2 monolayer, envisioned as a potential constituent layer in a Moiré-templated, strain-engineered vdW heterostructure of TMDs. The robustness and programmable nature of our approach arise from superlattice symmetry, energetics and mechanics. Our approach provides a new strategy for on-demand design of morphology and local strain in TMDs under mechanical deformation.

Processing bulk natural wood into a high-performance structural material.

Synthetic structural materials with exceptional mechanical performance suffer from either large weight and adverse environmental impact (for example, steels and alloys) or complex manufacturing processes and thus high cost (for example, polymer-based and biomimetic composites). Natural wood is a low-cost and abundant material and has been used for millennia as a structural material for building and furniture construction. However, the mechanical performance of natural wood (its strength and toughness) is unsatisfactory for many advanced engineering structures and applications. Pre-treatment with steam, heat, ammonia or cold rolling followed by densification has led to the enhanced mechanical performance of natural wood. However, the existing methods result in incomplete densification and lack dimensional stability, particularly in response to humid environments, and wood treated in these ways can expand and weaken. Here we report a simple and effective strategy to transform bulk natural wood directly into a high-performance structural material with a more than tenfold increase in strength, toughness and ballistic resistance and with greater dimensional stability. Our two-step process involves the partial removal of lignin and hemicellulose from the natural wood via a boiling process in an aqueous mixture of NaOH and Na2SO3 followed by hot-pressing, leading to the total collapse of cell walls and the complete densification of the natural wood with highly aligned cellulose nanofibres. This strategy is shown to be universally effective for various species of wood. Our processed wood has a specific strength higher than that of most structural metals and alloys, making it a low-cost, high-performance, lightweight alternative.

Catalyst-Free In Situ Carbon Nanotube Growth in Confined Space via High Temperature Gradient.

Carbonaceous materials, such as graphite, carbon nanotubes (CNTs), and graphene, are in high demand for a broad range of applications, including batteries, capacitors, and composite materials. Studies on the transformation between different types of carbon, especially from abundant and low-cost carbon to high-end carbon allotropes, have received surging interest. Here, we report that, without a catalyst or an external carbon source, biomass-derived amorphous carbon and defective reduced graphene oxide (RGO) can be quickly transformed into CNTs in highly confined spaces by high temperature Joule heating. Combined with experimental measurements and molecular dynamics simulations, we propose that Joule heating induces a high local temperature at defect sites due to the corresponding high local resistance. The resultant temperature gradient in amorphous carbon or RGO drives the migration of carbon atoms and promotes the growth of CNTs without using a catalyst or external carbon source. Our findings on the growth of CNTs in confined spaces by fast high temperature Joule heating shed light on the controlled transition between different carbon allotropes, which can be extended to the growth of other high aspect ratio nanomaterials.

Anisotropic, Transparent Films with Aligned Cellulose Nanofibers.

Transparent films or substrates are ubiquitously used in photonics and optoelectronics, with glass and plastics as traditional choice of materials. Transparent films made of cellulose nanofibers are reported recently. However, all these films are isotropic in nature. This work, for the first time, reports a remarkably facile and effective approach to fabricating anisotropic transparent films directly from wood. The resulting films exhibit an array of exceptional optical and mechanical properties. The well-aligned cellulose nanofibers in natural wood are maintained during delignification, leading to an anisotropic film with high transparency (≈90% transmittance) and huge intensity ratio of transmitted light up to 350%. The anisotropic film with well-aligned cellulose nanofibers has a mechanical tensile strength of up to 350 MPa, nearly three times of that of a film with randomly distributed cellulose nanofibers. Atomistic mechanics modeling further reveals the dependence of the film mechanical properties on the alignment of cellulose nanofibers through the film thickness direction. This study also demonstrates guided liquid transport in a mesoporous, anisotropic wood film and its possible application in enabling new nanoelectronic devices. These unique and highly desirable properties of the anisotropic transparent film can potentially open up a range of green electronics and nanofluidics.

Compressible, Dense, Three-Dimensional Holey Graphene Monolithic Architecture.

By creating holes in 2D nanosheets, tortuosity and porosity can be greatly tunable, which enables a fast manufacturing process (i.e., fast removal of gas and solvent) toward various nanostructures. We demonstrated outstanding compressibility of holey graphene nanosheets, which is impossible for pristine graphene. Holey graphene powder can be easily compressed into dense and strong monoliths with different shapes at room temperature without using any solvents or binders. The remarkable compressibility of holey graphene, which is in sharp contrast with pristine graphene, not only enables the fabrication of robust, dense graphene products that exhibit high density (1.4 g/cm3), excellent specific mechanical strength [18 MPa/(g/cm3)], and good electrical (130 S/cm) and thermal (20 W/mK) conductivities, but also provides a binder-free dry process that overcomes the disadvantages of wet processes required for fabrication of three-dimensional graphene products. Fundamentally different from graphite, the holey graphene products are both dense and porous, which can enable possible broader applications such as energy storage and gas separation membranes.

Carbon Welding by Ultrafast Joule Heating.

Carbon nanomaterials exhibit outstanding electrical and mechanical properties, but these superior properties are often compromised as nanomaterials are assembled into bulk structures. This issue of scaling limits the use of carbon nanostructures and can be attributed to poor physical contacts between nanostructures. To address this challenge, we propose a novel technique to build a 3D interconnected carbon matrix by forming covalent bonds between carbon nanostructures. High temperature Joule heating was applied to bring the carbon nanofiber (CNF) film to temperatures greater than 2500 K at a heating rate of 200 K/min to fuse together adjacent carbon nanofibers with graphitic carbon bonds, forming a 3D continuous carbon network. The bulk electrical conductivity of the carbon matrix increased four orders of magnitude to 380 S/cm with a sheet resistance of 1.75 Ω/sq. The high temperature Joule heating not only enables fast graphitization of carbon materials at high temperature, but also provides a new strategy to build covalently bonded graphitic carbon networks from amorphous carbon source. Because of the high electrical conductivity, good mechanical structures, and anticorrosion properties, the 3D interconnected carbon membrane shows promising applications in energy storage and electrocatalysis fields.

Ultra-fast self-assembly and stabilization of reactive nanoparticles in reduced graphene oxide films.

Nanoparticles hosted in conductive matrices are ubiquitous in electrochemical energy storage, catalysis and energetic devices. However, agglomeration and surface oxidation remain as two major challenges towards their ultimate utility, especially for highly reactive materials. Here we report uniformly distributed nanoparticles with diameters around 10 nm can be self-assembled within a reduced graphene oxide matrix in 10 ms. Microsized particles in reduced graphene oxide are Joule heated to high temperature (∼1,700 K) and rapidly quenched to preserve the resultant nano-architecture. A possible formation mechanism is that microsized particles melt under high temperature, are separated by defects in reduced graphene oxide and self-assemble into nanoparticles on cooling. The ultra-fast manufacturing approach can be applied to a wide range of materials, including aluminium, silicon, tin and so on. One unique application of this technique is the stabilization of aluminium nanoparticles in reduced graphene oxide film, which we demonstrate to have excellent performance as a switchable energetic material.

Reduced Graphene Oxide Films with Ultrahigh Conductivity as Li-Ion Battery Current Collectors.

Solution processed, highly conductive films are extremely attractive for a range of electronic devices, especially for printed macroelectronics. For example, replacing heavy, metal-based current collectors with thin, light, flexible, and highly conductive films will further improve the energy density of such devices. Films with two-dimensional building blocks, such as graphene or reduced graphene oxide (RGO) nanosheets, are particularly promising due to their low percolation threshold with a high aspect ratio, excellent flexibility, and low cost. However, the electrical conductivity of these films is low, typically less than 1000 S/cm. In this work, we for the first time report a RGO film with an electrical conductivity of up to 3112 S/cm. We achieve high conductivity in RGO films through an electrical current-induced annealing process at high temperature of up to 2750 K in less than 1 min of anneal time. We studied in detail the unique Joule heating process at ultrahigh temperature. Through a combination of experimental and computational studies, we investigated the fundamental mechanism behind the formation of a highly conductive three-dimensional structure composed of well-connected RGO layers. The highly conductive RGO film with high direct current conductivity, low thickness (∼4 µm) and low sheet resistance (0.8 Ω/sq.) was used as a lightweight current collector in Li-ion batteries.

Programmable Extreme Pseudomagnetic Fields in Graphene by a Uniaxial Stretch.

Many of the properties of graphene are tied to its lattice structure, allowing for tuning of charge carrier dynamics through mechanical strain. The graphene electromechanical coupling yields very large pseudomagnetic fields for small strain fields, up to hundreds of Tesla, which offer new scientific opportunities unattainable with ordinary laboratory magnets. Significant challenges exist in investigation of pseudomagnetic fields, limited by the nonplanar graphene geometries in existing demonstrations and the lack of a viable approach to controlling the distribution and intensity of the pseudomagnetic field. Here we reveal a facile and effective mechanism to achieve programmable extreme pseudomagnetic fields with uniform distributions in a planar graphene sheet over a large area by a simple uniaxial stretch. We achieve this by patterning the planar graphene geometry and graphene-based heterostructures with a shape function to engineer a desired strain gradient. Our method is geometrical, opening up new fertile opportunities of strain engineering of electronic properties of 2D materials in general.

Anomalous scaling law of strength and toughness of cellulose nanopaper.

The quest for both strength and toughness is perpetual in advanced material design; unfortunately, these two mechanical properties are generally mutually exclusive. So far there exists only limited success of attaining both strength and toughness, which often needs material-specific, complicated, or expensive synthesis processes and thus can hardly be applicable to other materials. A general mechanism to address the conflict between strength and toughness still remains elusive. Here we report a first-of-its-kind study of the dependence of strength and toughness of cellulose nanopaper on the size of the constituent cellulose fibers. Surprisingly, we find that both the strength and toughness of cellulose nanopaper increase simultaneously (40 and 130 times, respectively) as the size of the constituent cellulose fibers decreases (from a mean diameter of 27 µm to 11 nm), revealing an anomalous but highly desirable scaling law of the mechanical properties of cellulose nanopaper: the smaller, the stronger and the tougher. Further fundamental mechanistic studies reveal that reduced intrinsic defect size and facile (re)formation of strong hydrogen bonding among cellulose molecular chains is the underlying key to this new scaling law of mechanical properties. These mechanistic findings are generally applicable to other material building blocks, and therefore open up abundant opportunities to use the fundamental bottom-up strategy to design a new class of functional materials that are both strong and tough.

Mechanical Control of Graphene on Engineered Pyramidal Strain Arrays.

Strain can tune desirable electronic behavior in graphene, but there has been limited progress in controlling strain in graphene devices. In this paper, we study the mechanical response of graphene on substrates patterned with arrays of mesoscale pyramids. Using atomic force microscopy, we demonstrate that the morphology of graphene can be controlled from conformal to suspended depending on the arrangement of pyramids and the aspect ratio of the array. Nonuniform strains in graphene suspended across pyramids are revealed by Raman spectroscopy and supported by atomistic modeling, which also indicates strong pseudomagnetic fields in the graphene. Our results suggest that incorporating mesoscale pyramids in graphene devices is a viable route to achieving strain-engineering of graphene.

Hydrogenation-assisted graphene origami and its application in programmable molecular mass uptake, storage, and release.

The malleable nature of atomically thin graphene makes it a potential candidate material for nanoscale origami, a promising bottom-up nanomanufacturing approach to fabricating nanobuilding blocks of desirable shapes. The success of graphene origami hinges upon precise and facile control of graphene morphology, which still remains as a significant challenge. Inspired by recent progresses on functionalization and patterning of graphene, we demonstrate hydrogenation-assisted graphene origami (HAGO), a feasible and robust approach to enabling the formation of unconventional carbon nanostructures, through systematic molecular dynamics simulations. A unique and desirable feature of HAGO-enabled nanostructures is the programmable tunability of their morphology via an external electric field. In particular, we demonstrate reversible opening and closing of a HAGO-enabled graphene nanocage, a mechanism that is crucial to achieve molecular mass uptake, storage, and release. HAGO holds promise to enable an array of carbon nanostructures of desirable functionalities by design. As an example, we demonstrate HAGO-enabled high-density hydrogen storage with a weighted percentage exceeding the ultimate goal of US Department of Energy.

Novel nanostructured paper with ultrahigh transparency and ultrahigh haze for solar cells.

Solar cell substrates require high optical transparency but also prefer high optical haze to increase the light scattering and consequently the absorption in the active materials. Unfortunately, there is a trade-off between these optical properties, which is exemplified by common transparent paper substrates exhibiting a transparency of about 90% yet a low optical haze (<20%). In this work, we introduce a novel transparent paper made of wood fibers that displays both ultrahigh optical transparency (∼ 96%) and ultrahigh haze (∼ 60%), thus delivering an optimal substrate design for solar cell devices. Compared to previously demonstrated nanopaper composed of wood-based cellulose nanofibers, our novel transparent paper has better dual performance in transmittance and haze but also is fabricated at a much lower cost. This high-performance, low-cost transparent paper is a potentially revolutionary material that may influence a new generation of environmentally friendly printed electronics.

Electromechanical properties of graphene drumheads.

We determined the electromechanical properties of a suspended graphene layer by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) measurements, as well as computational simulations of the graphene-membrane mechanics and morphology. A graphene membrane was continuously deformed by controlling the competing interactions with a STM probe tip and the electric field from a back-gate electrode. The probe tip-induced deformation created a localized strain field in the graphene lattice. STS measurements on the deformed suspended graphene display an electronic spectrum completely different from that of graphene supported by a substrate. The spectrum indicates the formation of a spatially confined quantum dot, in agreement with recent predictions of confinement by strain-induced pseudomagnetic fields.