Tuning instability in suspended monolayer 2D materials.

Monolayer two-dimensional (2D) materials possess excellent in-plane mechanical strength yet extremely low bending stiffness, making them particularly susceptible to instability, which is anticipated to have a substantial impact on their physical functionalities such as 2D-based Micro/Nanoelectromechanical systems (M/NEMS), nanochannels, and proton transport membrane. In this work, we achieve quantitatively tuning instability in suspended 2D materials including monolayer graphene and MoS2 by employing a push-to-shear strategy. We comprehensively examine the dynamic wrinkling-splitting-smoothing process and find that monolayer 2D materials experience stepwise instabilities along with different recovery processes. These stepwise instabilities are governed by the materials' geometry, pretension, and the elastic nonlinearity. We attribute the different instability and recovery paths to the local stress redistribution in monolayer 2D materials. The tunable instability behavior of suspended monolayer 2D materials not only allows measuring their bending stiffness but also opens up new opportunities for programming the nanoscale instability pattern and even physical properties of atomically thin films.

Strain Engineering of Twisted Bilayer Graphene: The Rise of Strain-Twistronics.

The layer-by-layer stacked van der Waals structures (termed vdW hetero/homostructures) offer a new paradigm for materials design-their physical properties can be tuned by the vertical stacking sequence as well as by adding a mechanical twist, stretch, and hydrostatic pressure to the atomic structure. In particular, simple twisting and stacking of two layers of graphene can form a uniform and ordered Moiré superlattice, which can effectively modulate the electrons of graphene layers and lead to the discovery of unconventional superconductivity and strong correlations. However, the twist angle of twisted bilayer graphene (tBLG) is almost unchangeable once the interlayer stacking is determined, while applying mechanical elastic strain provides an alternative way to deeply regulate the electronic structure by controlling the lattice spacing and symmetry. In this review, diverse experimental advances are introduced in straining tBLG by in-plane and out-of-plane modes, followed by the characterizations and calculations toward quantitatively tuning the strain-engineered electronic structures. It is further discussed that the structural relaxation in strained Moiré superlattice and its influence on electronic structures. Finally, the conclusion entails prospects for opportunities of strained twisted 2D materials, discussions on existing challenges, and an outlook on the intriguing emerging field, namely "strain-twistronics".

Effect of Eccentricity Difference on the Mechanical Response of Microfluidics-Derived Hollow Silica Microspheres during Nanoindentation.

Hollow microspheres as the filler material of syntactic foams have been adopted in extensive practical applications, where the physical parameters and their homogeneity have been proven to be critical factors during the design process, especially for high-specification scenarios. Based on double-emulsion droplet templates, hollow microspheres derived from microfluidics-enabled soft manufacturing have been validated to possess well-controlled morphology and composition with a much narrower size distribution and fewer defects compared to traditional production methods. However, for more stringent requirements, the innate density difference between the core-shell solution of the double-emulsion droplet template shall result in the wall thickness heterogeneity of the hollow microsphere, which will lead to unfavorable mechanical performance deviations. To clarify the specific mechanical response of microfluidics-derived hollow silica microspheres with varying eccentricities, a hybrid method combining experimental nanoindentation and a finite element method (FEM) simulation was proposed. The difference in eccentricity can determine the specific mechanical response of hollow microspheres during nanoindentation, including crack initiation and the evolution process, detailed fracture modes, load-bearing capacity, and energy dissipation capability, which should shed light on the necessity of optimizing the concentricity of double-emulsion droplets to improve the wall thickness homogeneity of hollow microspheres for better mechanical performance.

In Situ TEM Characterization and Modulation for Phase Engineering of Nanomaterials.

Solid-state phase transformation is an intriguing phenomenon in crystalline or noncrystalline solids due to the distinct physical and chemical properties that can be obtained and modified by phase engineering. Compared to bulk solids, nanomaterials exhibit enhanced capability for phase engineering due to their small sizes and high surface-to-volume ratios, facilitating various emerging applications. To establish a comprehensive atomistic understanding of phase engineering, in situ transmission electron microscopy (TEM) techniques have emerged as powerful tools, providing unprecedented atomic-resolution imaging, multiple characterization and stimulation mechanisms, and real-time integrations with various external fields. In this Review, we present a comprehensive overview of recent advances in in situ TEM studies to characterize and modulate nanomaterials for phase transformations under different stimuli, including mechanical, thermal, electrical, environmental, optical, and magnetic factors. We briefly introduce crystalline structures and polymorphism and then summarize phase stability and phase transformation models. The advanced experimental setups of in situ techniques are outlined and the advantages of in situ TEM phase engineering are highlighted, as demonstrated via several representative examples. Besides, the distinctive properties that can be obtained from in situ phase engineering are presented. Finally, current challenges and future research opportunities, along with their potential applications, are suggested.

Lipidomic diversity and proxy implications of archaea from cold seep sediments of the South China Sea.

Cold seeps on the continental margins are characterized by intense microbial activities that consume a large portion of methane by anaerobic methanotrophic archaea (ANME) through anaerobic oxidation of methane (AOM). Although ANMEs are known to contain unique ether lipids that may have an important function in marine carbon cycling, their full lipidomic profiles and functional distribution in particular cold-seep settings are still poorly characterized. Here, we combined the 16S rRNA gene sequencing and lipidomic approaches to analyze archaeal communities and their lipids in cold seep sediments with distinct methane supplies from the South China Sea. The archaeal community was dominated by ANME-1 in the moderate seepage area with strong methane emission. Low seepage area presented higher archaeal diversity covering Lokiarchaeia, Bathyarchaeia, and Thermoplasmata. A total of 55 core lipids (CLs) and intact polar lipids (IPLs) of archaea were identified, which included glycerol dialkyl glycerol tetraethers (GDGTs), hydroxy-GDGTs (OH-GDGTs), archaeol (AR), hydroxyarchaeol (OH-AR), and dihydroxyarchaeol (2OH-AR). Diverse polar headgroups constituted the archaeal IPLs. High concentrations of dissolved inorganic carbon (DIC) with depleted δ13CDIC and high methane index (MI) values based on both CLs (MICL) and IPLs (MIIPL) indicate that ANMEs were active in the moderate seepage area. The ANME-2 and ANME-3 clades were characterized by enhanced glycosidic and phosphoric diether lipids production, indicating their potential role in coupling carbon and phosphurus cycling in cold seep ecosystems. ANME-1, though representing a smaller proportion of total archaea than ANME-2 and ANME-3 in the low seepage area, showed a positive correlation with MIIPL, indicating a different mechanism contributing to the IPL-GDGT pool. This also suggests that MIIPL could be a sensitive index to trace AOM activities performed by ANME-1. Overall, our study expands the understanding of the archaeal lipid composition in the cold seep and improves the application of MI using intact polar lipids that potentially link to extent ANME activities.

Ductile amorphous boron nitride microribbons.

The broad applications of ceramic materials in functional devices are often limited by their intrinsic brittleness. Amorphous boron nitride (a-BN), as a promising ceramic has shown high thermal stability and excellent dielectric properties that can be applied to microfabricated aerogel and nano dielectric layers, while its mechanical properties at small scales are yet to be studied. Here we report synthesized a-BN microribbons can have a uniform elongation at a breaking strain of more than 50% upon tension, exhibiting outstanding ductility. Such a-BN microribbons with lengths ranging from tens to hundreds of micro-meters were prepared via the small molecule precursors sol-gel method. Through in situ uniaxial tensile measurements, we demonstrated that a-BN microribbons also display a surprising flaw-tolerance behaviour. Combining high-resolution atomic characterization with molecular dynamics simulations, we reveal that the large tensile plasticity of a-BN originates from the topological deformation induced multiple energy-dissipation mechanisms including unfolding and reorientation of local curly h-BN layers and their interlayer debonding, slippage as well as the intralayer tearing. Our findings provide new insights to develop ductile amorphous covalent-bonded materials for emerging applications.

Retrieving Grain Boundaries in 2D Materials.

The coalescence of randomly distributed grains with different crystallographic orientations can result in pervasive grain boundaries (GBs) in 2D materials during their chemical synthesis. GBs not only are the inherent structural imperfection that causes influential impacts on structures and properties of 2D materials, but also have emerged as a platform for exploring unusual physics and functionalities stemming from dramatic changes in local atomic organization and even chemical makeup. Here, recent advances in studying the formation mechanism, atomic structures, and functional properties of GBs in a range of 2D materials are reviewed. By analyzing the growth mechanism and the competition between far-field strain and local chemical energies of dislocation cores, a complete understanding of the rich GB morphologies as well as their dependence on lattice misorientations and chemical compositions is presented. Mechanical, electronic, and chemical properties tied to GBs in different materials are then discussed, towards raising the concept of using GBs as a robust atomic-scale scaffold for realizing tailored functionalities, such as magnetism, luminescence, and catalysis. Finally, the future opportunities in retrieving GBs for making functional devices and the major challenges in the controlled formation of GB structures for designed applications are commented.

Three Dimensional Printing of Bioinspired Crossed-Lamellar Metamaterials with Superior Toughness for Syntactic Foam Substitution.

Biological materials such as conch shells with crossed-lamellar textures hold impressive mechanical properties due to their capability to realize effective crack control and energy dissipation through the structural synergy of interfacial modulus mismatch and lamellar orientation disparity. Integrating this mechanism with mechanical metamaterial design can not only avoid the catastrophic post-yield stress drop found in traditional architectural materials with uniform lattice structures but also effectively maintain the stress level and improve the energy absorption ability. Herein, a novel bioinspired design strategy that combines regional particularity and overall cyclicity is proposed to innovate the connotation of long-range periodicity inside the metamaterial, in which the node constraint gradient and crossed-lamellar struts corresponding to the core features of conch shells are able to guide the deformation sequence with a self-strengthening response during compression. Detailed in situ experiments and finite element analysis confirm that the rotated broad layer stacking can shorten and impede the shear bands, further transforming the deformation of bioinspired metamaterial into a progressive, hierarchical way, highlighted by the cross-layer hysteresis. Even based on a brittle polymeric resin, excellent specific energy absorption capacity [4544 kJ/kg] has been achieved in this architecture, which far exceeds the reported metal-based syntactic foams for two orders of magnitude. These results offer new opportunities for the bioinspired metamaterials to substitute the widespread syntactic foams in specific applications required for both lightweight and energy absorption.

Deep Elastic Strain Engineering of 2D Materials and Their Twisted Bilayers.

Conventionally, tuning materials' properties can be done through strategies such as alloying, doping, defect engineering, and phase engineering, while in fact mechanical straining can be another effective approach. In particular, elastic strain engineering (ESE), unlike conventional strain engineering mainly based on epitaxial growth, allows for continuous and reversible modulation of material properties by mechanical loading/unloading. The exceptional intrinsic mechanical properties (including elasticity and strength) of two-dimensional (2D) materials make them naturally attractive candidates for potential ESE applications. Here, we demonstrated that using the strain effect to modulate the physical and chemical properties toward novel functional device applications, which could be a general strategy for various 2D materials and their heterostructures. We then show how ultralarge, uniform elastic strain in free-standing 2D monolayers can permit deep elastic strain engineering (DESE), which can result in fundamentally changed electronic and optoelectronic properties for unconventional device applications. In addition to monolayers and van der Waals (vdW) heterostructures, we propose that DESE can be also applied to twisted bilayer graphene and other emerging twisted vdW structures, allowing for unprecedented functional 2D material applications.

3D Printed Template-Assisted Assembly of Additive-Free Ti3C2Tx MXene Microlattices with Customized Structures toward High Areal Capacitance.

Ti3C2Tx MXene is a promising material for electrodes in microsupercapacitors. Recent efforts have been made to fabricate MXene electrodes with designed structures using 3D printing to promote electrolyte permeation and ion diffusion. However, challenges remain in structural design diversity due to the strict ink rheology requirement and limited structure choices caused by existing extrusion-based 3D printing. Herein, additive-free 3D architected MXene aerogels are fabricated via a 3D printed template-assisted method that combines 3D printed hollow template and cation-induced gelation process. This method allows the use of MXene ink with a wide range of concentrations (5 to 150 mg mL-1) to produce MXene aerogels with high structural freedom, fine feature size (>50 µm), and controllable density (3 to 140 mg cm-3). Through structure optimization, the 3D MXene aerogel shows high areal capacitance of 7.5 F cm-2 at 0.5 mA cm-2 with a high mass loading of 54.1 mg cm-2. It also exhibits an ultrahigh areal energy density of 0.38 mWh cm-2 at a power density of 0.66 mW cm-2.