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Colloidal clay nanosheets obtained by the delamination of layered crystals of smectite-type clay minerals in water form liquid crystals because of their shape anisotropy. Loading of organic dyes onto the liquid crystalline clay nanosheets will enable novel photonic materials, where photofunctions of the loaded dye are controlled by the liquid crystallinity of the clay nanosheets. However, adsorption of organic dyes onto the nanosheets renders the nanosheet surfaces hydrophobic, and consequently, colloidal stability of the nanosheets is lost. In this study, this drawback is overcome by sandwiching cationic stilbazolium dyes between a pair of synthetic fluorohectorite nanosheets. This is realized by the preparation of stilbazolium-clay second-stage intercalation compounds characterized by intercalation of dye cations into every other interlayer space of the hectorite clay, where nonintercalated interlayer spaces are occupied by Na+ ions. The second-stage intercalation compounds are obtained by partial ion exchange of mother clay mineral incorporating Na+ ions in all of the interlayer spaces and delaminated from the Na+-containing interlayer spaces to form clay nanosheets sandwiching the dye molecules. Aqueous colloids of the dye-sandwiching clay nanosheets form colloidal liquid crystals, and the dye-sandwiching liquid crystalline clay nanosheets respond to an applied AC electric field to be aligned parallel to the electric field. The assembled structure of the dye-sandwiching clay nanosheets under the electric field is characterized by aligned discrete clay platelets, which is somewhat different from that of a colloidal liquid crystal of clay nanosheets without dye loading characterized by macroscopic liquid crystalline domains up to submillimeters. The electric alignment of the clay nanosheets induces alteration of light absorption of the sandwiched stilbazolium molecules, which verifies a strategy of constructing stimuli-responsive photonic materials of clay-organic hybrids.
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One-dimensional dissolution of a layered compound in a nonpolar organic solvent is reported for the first time. A high-aspect ratio fluorohectorite modified with a cationic surfactant (dioctadecyldimethylammonium) showed spontaneous delamination into monolayer nanosheets in chloroform.
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Creatures, such as Venus flytrap and hummingbirds, capable of rapid predation through snap-through transition, provide paradigms for the design of soft actuators and robots with fast actions. However, these artificial "snappers" usually need contact stimulations to trigger the flipping. Reported here is a constrained anisotropic poly(N-isopropylacrylamide) hydrogel showing fast snapping upon light stimulation. This hydrogel is prepared by flow-induced orientation of nanosheets (NSs) within a rectangular tube. The precursor containing gold nanoparticles is immediately exposed to UV light for photopolymerization to fix the ordered structure of NSs. Two ends of the slender gel are clamped to form a buckle with bistability nature, which snaps to the other side upon laser irradiation. Systematic experiments are conducted to investigate the influences of power intensity and irradiation angle of the laser, as well as thickness and buckle height of the gel, on the snapping behaviors. The fast snapping is further used to kick a plastic bead and control the switch state. Furthermore, synergetic or oscillated snapping of the gel with two buckles of opposite directions is realized by inclined irradiation of a laser or horizontal irradiation with two lasers, respectively. Such light-steered snapping of hydrogels should merit designing soft robots, energy harvests, etc.
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Self-sustained motions are widespread in biological systems by harvesting energy from surrounding environments, which inspire scientists to develop autonomous soft robots. However, most-existing soft robots require dynamic heterogeneous stimuli or complex fabrication with different components. Recently, control of topological geometry has been promising to afford soft robots with physical intelligence and thus life-like motions. Reported here are a series of closed twisted ribbon robots, which exhibit self-sustained flipping and rotation under constant light irradiation. Both Möbius strip and Seifert ribbon robots are devised for the first time by using an identical hydrogel, which responds to light irradiation on either side. Experiment and simulation results indicate that the self-regulated motions of the hydrogel robots are related to fast and reversible response of muscle-like gel, self-shadowing effect, and topology-facilitated refresh of light-exposed regions. The motion speeds and directions of the hydrogel robots can be tuned over a wide range. These closed twisted ribbon hydrogels are further applied to execute specific tasks in aqueous environments, such as collecting plastic balls, climbing a vertical rod, and transporting objects. This work presents new design principle for autonomous hydrogel robots by benefiting from material response and topology geometry, which may be inspirative for the robotics community.
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Inorganic nanotubes have attracted much attention due to their unique physicochemical properties. Nanotubes can be prepared by scrolling exfoliated nanosheets under ambient conditions. However, how the nanosheet scrolled in its colloidal state has not been experimentally visualized. In this paper, we directly observed the scrolling process of nanosheets upon adsorption of organic cations. Exfoliated flat nanosheets of niobate and clay in aqueous colloids were found to scroll by adding organic cations, such as exfoliation reagents, to the colloids. Employment of cationic stilbazolium dye enabled in situ observation of the dye adsorption and scrolling by optical microscopy based on changes in color and morphology of the nanosheets. The scrolling was promoted for nanosheets adsorbed with a stilbazolium dye with a longer alkyl chain, suggesting that the interaction between the hydrophobic parts of the dye cations is the driving force of the scrolling. This finding should encourage research on the formation of nanotubes from nanosheets and also provides important guidelines for the selection of appropriate exfoliation reagents when exfoliating nanosheets from layered crystals.
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Steering soft robots in a self-regulated manner remains a grand challenge, which often requires continuous symmetry breaking and recovery steps for persistent motion. Although structural morphology is found significant for robotic functions, geometric topology has rarely been considered and appreciated. Here we demonstrate a series of knotbots, namely hydrogel-based robots with knotted structures, capable of autonomous rolling and spinning/rotating motions. With symmetry broken by external stimuli and restored by self-regulation, the coupling between self-constraint-induced prestress and photothermal strain animates the knotbots continuously. Experiments and simulations reveal that nonequilibrium processes are regulated dynamically and cooperatively by self-constraints, active deformations, and self-shadowing effect of the photo-responsive gel. The active motions enable the knotbots to execute tasks including gear rotation and rod climbing. This work paves the way to devise advanced soft robots with self-regulated sustainable motions by harnessing the topology.
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2D transition metal carbides and nitrides (MXenes) suggest an uncommonly broad combination of important functionalities amongst 2D materials. Nevertheless, MXene suffers from facile oxidation and colloidal instability upon conventional water-based processing, thus limiting applicability. By experiments and theory, It is suggested that for stability and dispersibility, it is critical to select uncommonly high permittivity solvents such as N-methylformamide (NMF) and formamide (FA) (εr = 171, 109), unlike the classical solvents characterized by high dipole moment and polarity index. They also allow high MXene stacking order within thin films on carbon nanotube (CNT) substrates, showing very high Terahertz (THz) shielding effectiveness (SE) of 40-60 dB at 0.3-1.6 THz in spite of the film thinness < 2 µm. The stacking order and mesoscopic porosity turn relevant for THz-shielding as characterized by small-angle X-ray scattering (SAXS). The mechanistic understanding of stability and structural order allows guidance for generic MXene applications, in particular in telecommunication, and more generally processing of 2D materials.
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Metamaterials possess exotic properties that do not occur in nature and have attracted significant attention in research and engineering. Two decades ago, the field of metamaterials emerged from linear electromagnetism, and today it encompasses a wide range of aspects related to solid matter, including electromagnetic and optical, mechanical and acoustic, as well as unusual thermal or mass transport phenomena. Combining different material properties can lead to emergent synergistic functions applicable in everyday life. Nevertheless, making such metamaterials in a robust, facile, and scalable manner is still challenging. This paper presents an effective protocol allowing for metasurfaces offering a synergy between optical and thermal properties. It utilizes liquid crystalline suspensions of nanosheets comprising two transparent silicate monolayers in a double stack, where gold nanoparticles are sandwiched between the two silicate monolayers. The colloidally stable suspension of nanosheets was applied in nanometre-thick coatings onto various substrates. The transparent coatings serve as absorbers in the infrared spectrum allowing for the efficient conversion of sunlight into heat. The peculiar metasurface couples plasmon-enhanced adsorption with anisotropic heat conduction in the plane of the coating, both at the nanoscale. Processing of the coating is based on scalable and affordable wet colloidal processing instead of having to apply physical deposition in high vacuum or lithographic techniques. Upon solar irradiation, the colloidal metasurface is quickly (60% of the time taken for the non-coated glass) heated to the level where complete defogging is assured without sacrificing transparency in the visible range. The protocol is generally applicable allowing for intercalation of any nanoparticles covering a range of physical properties that are then inherited to colloidal nanosheets. Because of their large aspect ratio, the nanosheets will inevitably orient parallel to any surface. This will allow for a toolbox capable of mimicking metamaterial properties while assuring facile processing via dip coating or spray coating.
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To ensure the safety and performance of lithium-ion batteries (LIBs), a rational design and optimization of suitable cathode materials are crucial. Lithium nickel cobalt manganese oxides (NCM) represent one of the most popular cathode materials for commercial LIBs. However, they are limited by several critical issues, such as transition metal dissolution, formation of an unstable cathode-electrolyte interphase (CEI) layer, chemical instability upon air exposure, and mechanical instability. In this work, coating fabricated by self-assembly of osmotically delaminated sodium fluorohectorite (Hec) nanosheets onto NCM (Hec-NCM) in a simple and technically benign aqueous wet-coating process is reported first. Complete wrapping of NCM by high aspect ratio (>10 000) nanosheets is enabled through an electrostatic attraction between Hec nanosheets and NCM as well as by the superior mechanical flexibility of Hec nanosheets. The coating significantly suppresses mechanical degradation while forming a multi-functional CEI layer. Consequently, Hec-NCM delivers outstanding capacity retention for 300 cycles. Furthermore, due to the exceptional gas barrier properties of the few-layer Hec-coating, the electrochemical performance of Hec-NCM is maintained even after 6 months of exposure to the ambient atmosphere. These findings suggest a new direction of significantly improving the long-term stability and activity of cathode materials by creating an artificial CEI layer.
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The goal of reconciling all packaging requirements, e.g., mechanical resistance, transparency, flexibility, and gas barrier properties, is immensely challenging for packaging materials. Particularly, the combination of flexibility and good gas barrier properties poses a serious problem, especially when barrier requirements can only be met by lamination with a metal foil, metalization, or vapor-deposited ceramic layers, as all of these tend to be nonstretchable. In this work, we produced a stretchable nanocomposite barrier composed of one-dimensional (1D) crystalline (Bragg stack) barrier films composed of alternating layers of poly(ethylene glycol) (PEG) and synthetic sodium fluorohectorite (Hec) nanosheets. By sandwiching the Bragg stack type film between two plasticized poly(vinyl alcohol) (PVOH) layers, a waterborne laminate was obtained that outperforms commercial polymer materials in terms of water vapor permeability (WVP = 2.8 g mm m-2 day-1 bar-1 at 23 °C and 85% relative humidity), which is remarkable for an entirely water-soluble film. Moreover, no deterioration of barrier performance up to 10% elongation was observed, rendering the transparent self-standing laminate promising for thermoformed blister packaging, shrink wrap, or vacuum packaging. Besides the low WVP, the scalable and green processing method makes this technology auspicious for real-world applications.
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The fabrication of one-dimensional (1D) crystalline, monodomain nanocomposite films (hybrid Bragg stacks) is still limited to a few combinations of polymers and clay. The main reason is the segregation of clay and polymers driven by the entropic loss faced by the polymer confined in a narrow slit between the nanosheets. By exchanging synthetic sodium-fluorohectorite with vinylbenzyltrimethylammonium chloride, we succeeded in delaminating clay via 1D dissolution in N-methylformamide to obtain a liquid crystalline suspension. By combining this with bisphenol A glycerolate diacrylate, 1D crystalline nanocomposites could be obtained via photopolymerization of doctor bladed wet coatings. Infrared spectroscopy confirmed the co-polymerization of monomers and the organic modifier between the hectorite platelets. This single-phase hybrid material shows very low oxygen and water vapor transmission rates. The incorporation of the modified clay into the polymer leads to an oxygen transmission rate of 0.21 cm3 m-2 day-1 atm-1 at 50% r.h. and 23 °C and a water vapor transmission rate of 0.05 g m-2 day-1 for a coating of 3.7 µm, making this material appropriate for challenging packaging applications.
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Clay minerals are abundant in caprock formations for anthropogenic storage sites for CO2, and they are potential capture materials for CO2 postcombustion sequestration. We investigate the response to CO2 exposure of dried fluorohectorite clay intercalated with Li+, Na+, Cs+, Ca2+, and Ba2+. By in situ powder X-ray diffraction, we demonstrate that fluorohectorite with Na+, Cs+, Ca2+, or Ba2+ does not swell in response to CO2 and that Li-fluorohectorite does swell. A linear uptake response is observed for Li-fluorohectorite by gravimetric adsorption, and we relate the adsorption to tightly bound residual water, which exposes adsorption sites within the interlayer. The experimental results are supported by DFT calculations.
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Cellulose acetate (CA) was partially acrylated, and the resulting cellulose acetate acrylate (acryl-substitution degree of 0.2) underwent quantitative thio-Michael click reactions with various thiols. A toolbox of functional CA polymers was obtained in this way, and their properties were studied. The modification with fatty alkyl thiols led to hydrophobic materials with large water drop contact angles. Octadecylthio-, butoxycarbonylpropylthio-, and furanylthio-modifications formed highly transparent materials. The new derivative CAASFur disintegrated completely under industrial composting conditions. Films of modified CA polymers were cast and investigated in terms of barrier properties. The nanocomposite of CAAS18 compounded with a synthetic layered silicate (hectorite) of a large aspect ratio showed permeabilities as low as 0.09 g mm m-2 day-1 for water vapor and 0.16 cm3 mm m-2 day-1 atm-1 for oxygen. This portfolio of functional CA polymers opens the door to new applications.
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Bottom-up strategies for the production of well-defined nanostructures often rely on the self-assembly of anisotropic colloidal particles (nanowires and nanosheets). These building blocks can be obtained by delamination in a solvent of low-dimensionality crystallites. To optimize particle availability, determination of the delamination mechanism and the different organization stages of anisotropic particles in dispersion is essential. We address this fundamental issue by exploiting a recently developed system of fluorohectorite smectite clay mineral that delaminates in water, leading to colloidal dispersions of single-layer, very large (≈20 µm) clay sheets at high dilution. We show that when the clay crystallites are dispersed in water, they swell to form periodic one-dimensional stacks of fluorohectorite sheets with very low volume fraction (<1%) and therefore huge (≈100 nm) periods. Using optical microscopy and synchrotron X-ray scattering, we establish that these colloidal stacks bear strong similarities, yet subtle differences, with a smectic liquid-crystalline phase. Despite the high dilution, the colloidal stacks of sheets, called colloidal accordions, are extremely robust mechanically and can persist for years. Moreover, when subjected to AC electric fields, they rotate as solid bodies, which demonstrates their outstanding internal cohesion. Furthermore, our theoretical model captures the dependence of the stacking period on the dispersion concentration and ionic strength and explains, invoking the Donnan effect, why the colloidal accordions are kinetically stable over years and impervious to shear and Brownian motion. Because our model is not system specific, we expect that similar colloidal accordions frequently appear as an intermediate state during the delamination process of two-dimensional crystals in polar solvents.
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Eliminating topological defects to achieve monodomain liquid crystals is highly significant for the fundamental studies of soft matter and building long-range ordered materials. However, liquid crystals are metastable and sensitive to external stimuli, such as flow, confinement, and electromagnetic fields, which cause their intrinsic polycrystallinity and topological defects. Here, we achieve the monodomain liquid crystals of graphene oxide over 30 cm through boundary-free sheargraphy. The obtained monodomain liquid crystals exhibit large-area uniform alignment of sheets, which has the same optical polarized angle and intensity. The monodomain liquid crystals provide bidirectionally ordered skeletons, which can be applied as lightweight thermal management materials with bidirectionally high thermal and electrical conductivity. Furthermore, we extend the controllable topology of two-dimensional colloids by introducing singularities and disclinations in monodomain liquid crystals. Topological structures with defect strength from - 2 to + 2 were realized. This work provides a facile methodology to study the structural order of soft matter at a macroscopic level, facilitating the fabrication of metamaterials with tunable and highly anisotropic architectures.
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The transition dipole orientations of dye assemblies in heterostructures have a crucial impact on the efficiency of novel optoelectronic devices such as organic thin-film transistors and light-emitting diodes. These devices are frequently based on heterojunctions and tandem structures featuring multiple optical transitions. Precise knowledge of preferred orientations, spatial order, and spatial variations is highly relevant. We present a fast and universal large-area screening method to determine the transition dipole orientations in dye assemblies with diffraction-limited spatial resolution. Moreover, our hyperspectral imaging approach disentangles the orientations of different chromophores. As a demonstration, we apply our technique to dye monolayers with two optical transitions sandwiched between two ultrathin silicate nanosheets. A comprehensive model for dipole orientation distributions in monolayers reveals a long-range orientational order and a strong correlation between the two transitions.
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Swelling of clays is hampered by increasing layer charge. With vermiculite-type layer charge densities, crystalline swelling is limited to the two-layer hydrate, while osmotic swelling requires ion exchange with bulky and hydrophilic organic molecules or with Li+ cations to trigger repulsive osmotic swelling. Here, we report on surprising and counterintuitive osmotic swelling behavior of a vermiculite-type synthetic clay [Na0.7]inter[Mg2.3Li0.7]oct[Si4]tetO10F2 in mixtures of water and dimethyl sulfoxide (DMSO). Although swelling in pure water is restricted to crystalline swelling, with the addition of DMSO, osmotic swelling sets in at some threshold composition. Finally, when the DMSO concentration is increased further to 75 vol %, swelling is restricted again to crystalline swelling as expected. Repulsive osmotic swelling thus is observed in a narrow composition range of the binary water-DMSO mixture, where a freezing point suppression is observed. This suppression is related to DMSO and water molecules exhibiting strong interactions leading to stable molecular clusters. Based on this phenomenological observation, we hypothesize that the unexpected swelling behavior might be related to the formation of different complexes of interlayer cations being formed at different compositions. Powder X-ray diffraction and 23Na magic angle spinning-NMR evidence is presented that supports this hypothesis. We propose that the synergistic solvation of the interlayer sodium at favorable compositions exerts a steric pressure by the complexes formed in the interlayer. Concomitantly, the basal spacing is increased to a level, where entropic contributions of interlayer species lead to a spontaneous thermodynamically allowed one-dimensional dissolution of the clay stack.
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Reported here is a multi-response anisotropic poly(N-isopropylacrylamide) hydrogel developed by using a rotating magnetic field to align magnetic double stacks (MDSs) that are fixed by polymerization. The magneto-orientation of MDSs originates from the unique structure with γ-Fe2 O3 nanoparticles sandwiched by two silicate nanosheets. The resultant gels not only exhibit anisotropic optical and mechanical properties but also show anisotropic responses to temperature and light. Gels with complex ordered structures of MDSs are further devised by multi-step magnetic orientation and photolithographic polymerization. These gels show varied birefringence patterns with potentials as information materials, and can deform into specific configurations upon stimulations. Multi-gait motions are further realized in the patterned gel through dynamic deformation under spatiotemporal light and friction regulation by imposed magnetic force. The magneto-orientation assisted fabrication of hydrogels with anisotropic structures and additional functions should bring opportunities for gel materials in biomedical devices, soft actuators/robots, etc.
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Exploiting the full potential of layered materials for a broad range of applications requires delamination into functional nanosheets. Delamination via repulsive osmotic swelling is driven by thermodynamics and represents the most gentle route to obtain nematic liquid crystals consisting exclusively of single-layer nanosheets. This mechanism was, however, long limited to very few compounds, including 2:1-type clay minerals, layered titanates, or niobates. Despite the great potential of zeolites and their microporous layered counterparts, nanosheet production is challenging and troublesome, and published procedures implied the use of some shearing forces. Here, we present a scalable, eco-friendly, and utter delamination of the microporous layered silicate ilerite into single-layer nanosheets that extends repulsive delamination to the class of layered zeolites. As the sheet diameter is preserved, nematic suspensions with cofacial nanosheets of ≈9000 aspect ratio are obtained that can be cast into oriented films, e.g., for barrier applications.