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93,899 result(s) for "materials synthesis"
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Efficient metal ion sieving in rectifying subnanochannels enabled by metal–organic frameworks
Biological ion channels have remarkable ion selectivity, permeability and rectification properties, but it is challenging to develop artificial analogues. Here, we report a metal–organic framework-based subnanochannel (MOFSNC) with heterogeneous structure and surface chemistry to achieve these properties. The asymmetrically structured MOFSNC can rapidly conduct K + , Na + and Li + in the subnanometre-to-nanometre channel direction, with conductivities up to three orders of magnitude higher than those of Ca 2+ and Mg 2+ , equivalent to a mono/divalent ion selectivity of 10 3 . Moreover, by varying the pH from 3 to 8 the ion selectivity can be tuned further by a factor of 10 2 to 10 4 . Theoretical simulations indicate that ion–carboxyl interactions substantially reduce the energy barrier for monovalent cations to pass through the MOFSNC, and thus lead to ultrahigh ion selectivity. These findings suggest ways to develop ion selective devices for efficient ion separation, energy reservation and power generation. Here, using an interfacial growth strategy, UiO-66 MOF nanocrystals are asymmetrically embedded into conical pores in a polymer membrane. These pores have a mono/divalent cation selectivity of 10 3 , which can be tuned by pH, and act as ionic rectifiers.
Tuning superconductivity in twisted bilayer graphene
Materials with flat electronic bands often exhibit exotic quantum phenomena owing to strong correlations. An isolated low-energy flat band can be induced in bilayer graphene by simply rotating the layers by 1.1°, resulting in the appearance of gate-tunable superconducting and correlated insulating phases. In this study, we demonstrate that in addition to the twist angle, the interlayer coupling can be varied to precisely tune these phases. We induce superconductivity at a twist angle larger than 1.1°—in which correlated phases are otherwise absent—by varying the interlayer spacing with hydrostatic pressure. Our low-disorder devices reveal details about the superconducting phase diagram and its relationship to the nearby insulator. Our results demonstrate twisted bilayer graphene to be a distinctively tunable platform for exploring correlated states.
Printing soft matter in three dimensions
Light- and ink-based three-dimensional (3D) printing methods allow the rapid design and fabrication of materials without the need for expensive tooling, dies or lithographic masks. They have led to an era of manufacturing in which computers can control the fabrication of soft matter that has tunable mechanical, electrical and other functional properties. The expanding range of printable materials, coupled with the ability to programmably control their composition and architecture across various length scales, is driving innovation in myriad applications. This is illustrated by examples of biologically inspired composites, shape-morphing systems, soft sensors and robotics that only additive manufacturing can produce.
Tunable crystal symmetry in graphene–boron nitride heterostructures with coexisting moiré superlattices
In van der Waals (vdW) heterostructures consisting of atomically thin crystals layered on top of one another, lattice mismatch and rotation between the layers can result in long-wavelength moiré superlattices. These moiré patterns can drive notable band structure reconstruction of the composite material, leading to a wide range of emergent phenomena including superconductivity1–3, magnetism4, fractional Chern insulating states5 and moiré excitons6–9. Here, we investigate devices consisting of monolayer graphene encapsulated between two crystals of boron nitride (BN), in which the rotational alignment of all three components is controlled. We find that bandgaps in the graphene arising from perfect rotational alignment with both BN layers can be modified considerably depending on whether the relative orientation of the two BN layers is 0° or 60°, suggesting a tunable transition between the absence or presence of inversion symmetry in the heterostructure. Small deviations (<1°) from perfect alignment of all three layers leads to coexisting long-wavelength moiré potentials, resulting in a highly reconstructed graphene band structure featuring multiple secondary Dirac points. Our results demonstrate that the interplay between multiple moiré patterns can be utilized to controllably modify the symmetry and electronic properties of the composite heterostructure.
Large linear-in-temperature resistivity in twisted bilayer graphene
Twisted bilayer graphene has recently emerged as a platform for hosting correlated phenomena. For twist angles near θ ≈ 1.1°, the low-energy electronic structure of twisted bilayer graphene features isolated bands with a flat dispersion1,2. Recent experiments have observed a variety of low-temperature phases that appear to be driven by electron interactions, including insulating states, superconductivity and magnetism3–6. Here we report electrical transport measurements up to room temperature for twist angles varying between 0.75° and 2°. We find that the resistivity, ρ, scales linearly with temperature, T, over a wide range of T before falling again owing to interband activation. The T-linear response is much larger than observed in monolayer graphene for all measured devices, and in particular increases by more than three orders of magnitude in the range where the flat band exists. Our results point to the dominant role of electron–phonon scattering in twisted bilayer graphene, with possible implications for the origin of the observed superconductivity.
Kinetic pathways of crystallization at the nanoscale
Nucleation and growth are universally important in systems from the atomic to the micrometre scale as they dictate structural and functional attributes of crystals. However, at the nanoscale, the pathways towards crystallization have been largely unexplored owing to the challenge of resolving the motion of individual building blocks in a liquid medium. Here we address this gap by directly imaging the full transition of dispersed gold nanoprisms to a superlattice at the single-particle level. We utilize liquid-phase transmission electron microscopy at low dose rates to control nanoparticle interactions without affecting their motions. Combining particle tracking with Monte Carlo simulations, we reveal that positional ordering of the superlattice emerges from orientational disorder. This method allows us to measure parameters such as line tension and phase coordinates, charting the nonclassical nucleation pathway involving a dense, amorphous intermediate. We demonstrate the versatility of our approach via crystallization of different nanoparticles, pointing the way to more general applications. Low-dose liquid-phase transmission electron microscopy, particle tracking and numerical simulations are used to characterize the crystallization kinetics and pathways of gold nanoprisms at the single-particle level.
Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal–organic framework nanocrystals
The dispersion of metal–organic framework nanocrystals within a polyimide yields membranes for selective chemical separations with strong resistance to plasticization. The implementation of membrane-based separations in the petrochemical industry has the potential to reduce energy consumption significantly relative to conventional separation processes 1 . Achieving this goal, however, requires the development of new membrane materials with greater selectivity, permeability and stability than available at present. Here, we report composite materials consisting of nanocrystals of metal–organic frameworks dispersed within a high-performance polyimide, which can exhibit enhanced selectivity for ethylene over ethane, greater ethylene permeability and improved membrane stability. Our results suggest that framework–polymer interactions reduce chain mobility of the polymer while simultaneously boosting membrane separation performance. The increased stability, or plasticization resistance, is expected to improve membrane utility under real process conditions for petrochemical separations and natural gas purification. Furthermore, this approach can be broadly applied to numerous polymers that encounter aggressive environments, potentially making gas separations possible that were previously inaccessible to membranes.
Recent progress in the synthesis of metal-organic frameworks
Metal-organic frameworks (MOFs) have attracted considerable attention for various applications due to their tunable structure, porosity and functionality. In general, MOFs have been synthesized from isolated metal ions and organic linkers under hydrothermal or solvothermal conditions via one-spot reactions. The emerging precursor approach and kinetically tuned dimensional augmentation strategy add more diversity to this field. In addition, to speed up the crystallization process and create uniform crystals with reduced size, many alternative synthesis routes have been explored. Recent advances in microwave-assisted synthesis and electrochemical synthesis are presented in this review. In recent years, post-synthetic approaches have been shown to be powerful tools to synthesize MOFs with modified functionality, which cannot be attained via de novo synthesis. In this review, some current accomplishments of post-synthetic modification (PSM) based on covalent transformations and coordinative interactions as well as post-synthetic exchange (PSE) in robust MOFs are provided.
Low-loss composite photonic platform based on 2D semiconductor monolayers
The optical properties of transition metal dichalcogenides (TMDs) are known to change dramatically with doping near their excitonic resonances. However, little is known about the effect of doping on the optical properties of TMDs at wavelengths far from these resonances, where the material is transparent and therefore could be leveraged in photonic circuits. We demonstrate the strong electrorefractive response of monolayer tungsten disulfide (WS2) at near-infrared wavelengths (deep in the transparency regime) by integrating it on silicon nitride photonic structures to enhance the light–matter interaction with the monolayer. We show that the doping-induced phase change relative to the change in absorption (|∆n/∆k|) is ~125, which is significantly higher than the |∆n/∆k| observed in materials commonly employed for silicon photonic modulators, including Si and III–V on Si, while accompanied by negligible insertion loss.Strong electrorefractive effects in semiconductor transition metal dichalcogenides (TMDs) at near-infrared wavelengths, where the TMDs are transparent, are observed and used to demonstrate photonic devices based on a composite SiN–TMD platform with large phase modulation, minimal induced loss and low electrical power consumption.