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Freestanding functional inorganic membranes, beyond the limits of their organic and polymeric counterparts1, may unlock the potentials of advanced separation2, catalysis3, sensors4,5, memories6, optical filtering7 and ionic conductors8,9. However, the brittle nature of most inorganic materials, and the lack of surface unsaturated linkages10, mean that it is difficult to form continuous membranes through conventional top-down mouldings and/or bottom-up syntheses11. Up to now, only a few specific inorganic membranes have been fabricated from predeposited films by selective removal of sacrificial substrates4-6,8,9. Here we demonstrate a strategy to switch nucleation preferences in aqueous systems of inorganic precursors, resulting in the formation of various ultrathin inorganic membranes at the air-liquid interface. Mechanistic study shows that membrane growth depends on the kinematic evolution of floating building blocks, which helps to derive the phase diagram based on geometrical connectivity. This insight provides general synthetic guidance towards any unexplored membranes, as well as the principle of tuning membrane thickness and through-hole parameters. Beyond understanding a complex dynamic system, this study comprehensively expands the traditional notion of membranes in terms of composition, structure and functionality.
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Adhesive materials have recently drawn intensive attention due to their excellent sealing ability, thereby stimulating advances in materials science and industrial usage. However, reported adhesives usually exhibit weak adhesion strength, require high pressure for strong bonding, and display severe adhesion deterioration in various harsh environments. In this work, instead of water or organic solvents, a deep eutectic solution (DES) was used as the medium for photopolymerization of zwitterionic and polarized monomers, thus generating a novel ionogel with tunable mechanical properties. Multiple hydrogen bonds and electrostatic interactions between DES and monomers facilitated ultrafast gelation and instant bonding without any external pressure, which was rarely reported previously. Furthermore, high adhesion in different harsh environments (e.g., water, acidic and basic buffers, and saline solutions) and onto hydrophilic (e.g., glass and tissues) and hydrophobic (e.g., polymethyl methacrylate, polystyrene, and polypropylene) adherends was demonstrated. Also, high stretchability of the ionogel at extreme temperatures (-80 and 80 °C) indicated its widespread applications. Furthermore, the biocompatible ionogel showed high burst pressure onto stomach and intestine tissues to prevent liquid leakage, highlighting its potential as an adhesive patch. This ionogel provides unprecedented opportunities in the fields of packaging industry, marine engineering, medical adhesives, and electronic assembly.
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Optimizing catalysts for competitive photocatalytic reactions demand individually tailored band structure as well as intertwined interactions of light absorption, reaction activity, mass, and charge transport. Here, a nanoparticulate host-guest structure is rationally designed that can exclusively fulfil and ideally control the aforestated uncompromising requisites for catalytic reactions. The all-inclusive model catalyst consists of porous Co3 O4 host and Znx Cd1- x S guest with controllable physicochemical properties enabled by self-assembled hybrid structure and continuously amenable band gap. The effective porous topology nanoassembly, both at the exterior and the interior pores of a porous metal-organic framework (MOF), maximizes spatially immobilized semiconductor nanoparticles toward high utilization of particulate heterojunctions for vital charge and reactant transfer. In conjunction, the zinc constituent band engineering is found to regulate the light/molecules absorption, band structure, and specific reaction intermediates energy to attain high photocatalytic CO2 reduction selectivity. The optimal catalyst exhibits a H2 -generation rate up to 6720 µmol g-1 h-1 and a CO production rate of 19.3 µmol g-1 h-1 . These findings provide insight into the design of discrete host-guest MOF-semiconductor hybrid system with readily modulated band structures and well-constructed heterojunctions for selective solar-to-chemical conversion.
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Though plasmonic effect is making some headway in the energy harvesting realm, its fundamental charge transfer mechanism to a large extent is attributed to the hot-carrier generation at the contact interface. Herein this work attempts to elucidate the physical origin of light induced plasmo-pyroelectric enhancement based on charge density manipulation on surface state in the vicinity of the metal-ferroelectric contact interface. More importantly, by tuning the band bending, it is shown that the charge density on the surface state of a hybrid plasmo-pyroelectric (BaTiO3 -Ag) nanosystem can be manipulated and largely increased under the resonant blue light illumination (363 nm). It is also demonstrated that owing to this effect, the spatial pyroelectric activity of a hybrid plasmo-pyroelectric nanosystem governs 46% enhancement in pyroelectric coefficient. This research highlights the optically regulated charge density in plasmo-pyroelectric nanosystems, which could pave a new avenue for energy harvesting/conversion devices with distinguished advantages in wireless, photonic-controlled, localized, and dynamic stimulation.
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A persistent challenge in classical photocatalyst systems with extended light absorption is the unavoidable trade-off between maximizing light harvesting and sustaining high photoredox capability. Alternatively, cooperative energy conversion through photothermic activation and photocatalytic redox is a promising yet unmet scientific proposition that critically demands a spectrum-tailored catalyst system. Here, we construct a solar thermal-promoted photocatalyst, an ultrathin "biphasic" ordered-disordered D-HNb3 O8 junction, which performs two disparate spectral selective functions of photoexcitation by ordered structure and thermal activated conversion via disordered lattice for combinatorial photothermal mediated catalysis. This inâ situ synthetically immobilized lattice distortion, constrained to a single-entity monolayer structure not only circumvents interfacial incompatibility but also triggers near-field temperature rise at the catalyst-reactant complexes' proximity to promote photoreaction. Ultimately, a generic full solar conversion improvement for H2 fuel production, organic transformation and water purification is realized.
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The fast development of nanoscience and nanotechnology has significantly advanced the fabrication of nanocatalysts and the in-depth study of the structural-activity characteristics of materials at the atomic level. Vacancies, as typical atomic defects or imperfections that widely exist in solid materials, are demonstrated to effectively modulate the physicochemical, electronic, and catalytic properties of nanomaterials, which is a key concept and hot research topic in nanochemistry and nanocatalysis. The recent experimental and theoretical progresses achieved in the preparation and application of vacancy-rich nanocatalysts for electrochemical water splitting are explored. Engineering of vacancies has shown to open up a new avenue beyond the traditional morphology, size, and composition modifications for the development of nonprecious electrocatalysts toward efficient energy conversion. First, an introduction followed by discussions of different types of vacancies, the approaches to create vacancies, and the advanced techniques widely used to characterize these vacancies are presented. Importantly, the correlations between the vacancies and activities of the vacancy-rich electrocatalysts via tuning the electronic states, active sites, and kinetic energy barriers are reviewed. Finally, perspectives on the existing challenges along with some opportunities for the further development of vacancy-rich noble metal-free electrocatalysts with high performance are discussed.
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Surface plasmon-based photonics offers exciting opportunities to enable fine control of the site, span, and extent of mechanical harvesting. However, the interaction between plasmonic photothermic and piezoresponse still remains underexplored. Here, spatially localized and controllable piezoresponse of a hybrid self-polarized polymeric-metallic system that correlates to plasmonic light-to-heat modulation of the local strain is demonstrated. The piezoresponse is associated to the localized plasmons that serve as efficient nanoheaters leading to self-regulated strain via thermal expansion of the electroactive polymer. Moreover, the finite-difference time-domain simulation and linear thermal model also deduce the local strain to the surface plasmon heat absorption. The distinct plasmonic photothermic-piezoelectric phenomenon mediates not only localized external stimulus light response but also enhances dynamic piezoelectric energy harvesting. The present work highlights a promising surface plasmon coordinated piezoelectric response which underpins energy localization and transfer for diversified design of unique photothermic-piezotronic technology.
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Nanotecnologia/métodos , Polímeros/química , Nanoestruturas/química , Ressonância de Plasmônio de SuperfícieRESUMO
Large-area, 2D, anisotropic, direct growth of nanostructures is considered an effective and straightforward way to readily fulfill transparent, flexible technology requirements. In addition, formation of thin hybrid structures by combining with another 2D material brings about dimensional advantages, such as intimate heterostructure functionalities, large specific area, and optical transparency. Here, we demonstrate 2D planar growth of thin Ni(OH)2 nanosheets on arbitrary rigid and soft supports, by exploiting the growth strategies of oriented attachment induced by interfacial chemistry and the intrinsic driving force of layered structure constitution. Moreover, large-scale 2D heterohybrids have successfully been prepared by direct conformal growth of Ni(OH)2 nanosheets overlying MoO3 nanobelts. Unlike the exfoliation and transfer of 2D materials technique, this approach minimizes multiple process contamination and physical-handling structural defects. Accordingly, proof-of-concept flexible electrochromism is demonstrated in view of its prerequisite to the access of a large homogeneous material coating. The as-synthesized 2D layered structure affirms its optical and electrochemical superiority through the display of wide optical modulation, high coloration efficiency, good cyclic stability, and flexibility.
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We present a room temperature topotactic consolidation of cobalt and zinc constituents into monocrystalline CoZn hydroxide nanosheets, by a localized corrosion of zinc foils with cobalt precursors. By virtue of similar lattice orientation and structure coordination, the hybrid hydroxides amalgamate atomically without phase separation. Importantly, this inâ situ growth strategy, in combination with configurable percolated nanosheets, renders a high areal density of catalytic sites, immobilized structures, and conductive pathways between the nanosheets and underlying foils-all of which allow monocrystalline CoZn hydroxide nanosheet materials to function as effective electrodes for electrochemical oxygen evolution reactions. This convenient and eco-friendly topotactical transformation approach facilitates high-quality single crystal growth with improved multiphase purity and homogeneity, which can be extended to other transition metals for the fabrication of advanced functional nanocomposites.
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Inexpensive and readily available metal foils have been extracted and sculptured into nanocomposites without the expense of applied energy. The unwanted corrosion phenomenon has been contrarily utilized to realize desirable 3D nanostructures through a corrosion-mediated self-assembly (CMSA) method, which is unattainable by conventional 2D patterning routes. By virtue of electrochemical dissolution/re-deposition initiated by brass corrosion, ionic derivatives (Zn(2+) and Cu(2+) ) are continuously supplied and seized by etchant ions (PO4 (3-) ) to self-assemble into well-defined nanocomposites. Beyond 3D geometry patterning, CMSA enables arbitrarily tailoring of structures and chemical compositions with inâ situ multiphase amalgamation of hybrid materials, which improves homogeneity and thus mitigates phase separation issues. Importantly, the CMSA technique is demonstrated on transition metals for functional photocatalytic applications.
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For the first time an earth-abundant and nontoxic ZnS-Cu(1.8) S hybrid photocatalyst has been engineered with well-defined nanosheet hollow structures by a template-engaged method. In contrast to conventional surface coupling and loading, the unique outside-in recrystallization promotes co-precipitation of ZnS and Cu(1.8) S into homogeneous interdispersed lattices, hence forming a hybrid semiconductor with visible responsive photocatalytic activity. The as-derived ZnS-Cu(1.8) S semiconductor alloy is tailored into a hierarchical hollow structure to provide readily accessible porous shells and interior spaces for effective ion transfer/exchange. Notably, this synergistic morphology, interface and crystal lattice engineering, aim towards the design of novel nanocatalysts for various sustainable environmental and energy applications.
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Compliant strain sensors are crucial for soft robots' perception and autonomy. However, their deformable bodies and dynamic actuation pose challenges in predictive sensor manufacturing and long-term robustness. This necessitates accurate sensor modelling and well-controlled sensor structural changes under strain. Here, we present a computational sensor design featuring a programmed crack array within micro-crumples strategy. By controlling the user-defined structure, the sensing performance becomes highly tunable and can be accurately modelled by physical models. Moreover, they maintain robust responsiveness under various demanding conditions including noise interruptions (50% strain), intermittent cyclic loadings (100,000 cycles), and dynamic frequencies (0-23 Hz), satisfying soft robots of diverse scaling from macro to micro. Finally, machine intelligence is applied to a sensor-integrated origami robot, enabling robotic trajectory prediction (<4% error) and topographical altitude awareness (<10% error). This strategy holds promise for advancing soft robotic capabilities in exploration, rescue operations, and swarming behaviors in complex environments.
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Hydrogels possess unique features such as softness, wetness, responsiveness, and biocompatibility, making them highly suitable for biointegrated applications that have close interactions with living organisms. However, conventional man-made hydrogels are usually soft and brittle, making them inferior to the mechanically robust biological hydrogels. To ensure reliable and durable operation of biointegrated wearable and implantable devices, mechanical matching and shape adaptivity of hydrogels to tissues and organs are essential. Recent advances in polymer science and processing technologies have enabled mechanical engineering and shaping of hydrogels for various biointegrated applications. In this review, polymer network structuring strategies at micro/nanoscales for toughening hydrogels are summarized, and representative mechanical functionalities that exist in biological materials but are not easily achieved in synthetic hydrogels are further discussed. Three categories of processing technologies, namely, 3D printing, spinning, and coating for fabrication of tough hydrogel constructs with complex shapes are reviewed, and the corresponding hydrogel toughening strategies are also highlighted. These developments enable adaptive fabrication of mechanically robust and functional hydrogel devices, and promote application of hydrogels in the fields of biomedical engineering, bioelectronics, and soft robotics.
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Hidrogéis , Dispositivos Eletrônicos Vestíveis , Hidrogéis/química , Humanos , Materiais Biocompatíveis/química , Impressão Tridimensional , Próteses e Implantes , Polímeros/química , Animais , Fenômenos Mecânicos , RobóticaRESUMO
Weather-adaptive energy harvesting of omnipresent waste heat and rain droplets, though promising in the field of environmental energy sustainability, is still far from practice due to its low electrical output owing to dielectric structure irrationality and unscalability. Here we present atypical upcycling of ambient heat and raindrop energy via an all-in-one non-planar energy harvester, simultaneously increasing solar pyroelectricity and droplet-based triboelectricity by two-fold, in contrast to conventional counterparts. The delivered non-planar dielectric with high transmittance confines the solar irradiance onto a focal hotspot, offering transverse thermal field propagation towards boosted inhomogeneous polarization with a generated power density of 6.1 mW m-2 at 0.2 sun. Moreover, the enlarged lateral surface area of curved architecture promotes droplet spreading/separation, thus travelling the electrostatic field towards increased triboelectricity. These enhanced pyroelectric and triboelectric outputs, upgraded with advanced manufacturing, demonstrate applicability in adaptive sustainable energy harvesting on sunny, cloudy, night, and rainy days. Our findings highlight a facile yet efficient strategy, not only for weather-adaptive environmental energy recovery but also in providing key insights for spatial thermal/electrostatic field manipulation in thermoelectrics and ferroelectrics.
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Flexible thermoelectric harvesting of omnipresent spatial thermodynamic energy, though promising in low-grade waste heat recovery (<100°C), is still far from industrialization because of its unequivocal cost-ineffectiveness caused by low thermoelectric efficiency and power-cost coupled device topology. Here, we demonstrate unconventional upcycling of low-grade heat via physics-guided rationalized flexible thermoelectrics, without increasing total heat input or tailoring material properties, into electricity with a power-cost ratio (W/US$) enhancement of 25.3% compared to conventional counterparts. The reduced material usage (44%) contributes to device power-cost "decoupling," leading to geometry-dependent optimal electrical matching for output maximization. This offers an energy consumption reduction (19.3%), electricity savings (0.24 kWh W-1), and CO2 emission reduction (0.17 kg W-1) for large-scale industrial production, fundamentally reshaping the R&D route of flexible thermoelectrics for techno-economic sustainable heat harvesting. Our findings highlight a facile yet cost-effective strategy not only for low-grade heat harvesting but also for electronic co-design in heat management/recovery frontiers.
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Pyroelectricity originates from spontaneous polarization variation, promising in omnipresent non-static thermodynamic energy harvesting. Particularly, changing spontaneous polarization via out-of-plane uniform heat perturbations has been shown in solar pyroelectrics. However, these approaches present unequivocal inefficiency due to spatially coupled low temperature change and duration along the longitudinal direction. Here we demonstrate unconventional giant polarization ripples in transverse pyroelectrics, without increasing the total energy input, into electricity with an efficiency of 5-fold of conventional longitudinal counterparts. The non-uniform graded temperature variation arises from decoupled heat localization and propagation, leading to anomalous in-plane heat perturbation (29-fold) and enhanced thermal disequilibrium effects. This in turn triggers an augmented polarization ripple, fundamentally enabling unprecedented electricity generation performance. Notably, the device generates a power density of 38 mW m-2 at 1 sun illumination, which is competitive with solar thermoelectrics and ferrophotovoltaics. Our findings provide a viable paradigm, not only for universal practical pyroelectric heat harvesting but for flexible manipulation of transverse heat transfer towards sustainable energy harvesting and management.
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On-skin patches that record biopotential and biomechanical signals are essential for wearable healthcare monitoring, clinical treatment, and human-machine interaction. To acquire wearing comfort and high-quality signals, patches with tissue-like softness, elastic recovery, damage tolerance, and robust bioelectronic interface are highly desired yet challenging to achieve. Here, we report a dry epidermal patch made from a supramolecular polymer (SESA) and an in situ transferred carbon nanotubes' percolation network. The polymer possesses a hybrid structure of copolymerized permanent scaffold permeated by multiple dynamic interactions, which imparts a desired mechanical response transition from elastic recoil to energy dissipation with increased elongation. Such SESA-based patches are soft (Young's modulus â¼0.1 MPa) and elastic within physiologically relevant strain levels (97% elastic recovery at 50% tensile strain), intrinsically mechanical-electrical damage-resilient (â¼90% restoration from damage after 5 min), and interference-immune in dynamic signal acquisition (stretch, underwater, sweat). We demonstrate its versatile physiological sensing applications, including electrocardiogram recording under various disturbances, machine-learning-enabled hand-gesture recognition through electromyogram measurement, subtle radial artery pulse, and drastic knee kinematics sensing. This epidermal patch offers a promising noninvasive, long-duration, and ambulant bioelectronic interfacing with anti-interference robustness.
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Nanotubos de Carbono , Humanos , Nanotubos de Carbono/química , Pele , Suor , Módulo de Elasticidade , Polímeros/químicaRESUMO
Mechanical properties of hydrogels are crucial to emerging devices and machines for wearables, robotics and energy harvesters. Various polymer network architectures and interactions have been explored for achieving specific mechanical characteristics, however, extreme mechanical property tuning of single-composition hydrogel material and deployment in integrated devices remain challenging. Here, we introduce a macromolecule conformational shaping strategy that enables mechanical programming of polymorphic hydrogel fiber based devices. Conformation of the single-composition polyelectrolyte macromolecule is controlled to evolve from coiling to extending states via a pH-dependent antisolvent phase separation process. The resulting structured hydrogel microfibers reveal extreme mechanical integrity, including modulus spanning four orders of magnitude, brittleness to ultrastretchability, and plasticity to anelasticity and elasticity. Our approach yields hydrogel microfibers of varied macromolecule conformations that can be built-in layered formats, enabling the translation of extraordinary, realistic hydrogel electronic applications, i.e., large strain (1000%) and ultrafast responsive (~30 ms) fiber sensors in a robotic bird, large deformations (6000%) and antifreezing helical electronic conductors, and large strain (700%) capable Janus springs energy harvesters in wearables.
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Hidrogéis , Polímeros , Elasticidade , PolieletrólitosRESUMO
Electronic structures, magnetic properties, and spin-dependent electron transport characteristics of C-doped ZnO nanowires have been investigated via first-principles method based on density functional theory and nonequilibrium techniques of Green's functions. Our calculations show that the doping of carbon atoms in a ZnO nanowire could induce strong magnetic moments in the wire, and the electronic structures as well as the magnetic properties of the system sensitively depend on partial hydrogenation. Based on these findings, we proposed a quasi-1d tunneling magnetic junction made of a partially hydrogenated C-doped ZnO nanowire, which shows a high tunneling magnetoresistance ratio, and could be the building block of a new class of spintronic devices.
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Freshwater production is one of the biggest global challenges today. Though desalination can provide a climate-independent source of clean water, the process requires a high energy consumption. Emerging advancement of photothermal nanomaterials and the urgent demand for a green technology transition have reinvigorated the established solar distillation technology. The current development of photothermal vaporization focuses on material innovation and interfacial heating, which largely emphasizes vapor generation efficiency, without considering pragmatic water collection. Moreover, salt accumulation is another critical issue of seawater solar-driven vaporization. The incorporation of photothermal materials into a photothermal membrane distillation (PMD) solar evaporator design harmoniously resolves these issues through combination of renewable energy and efficient interfacial distillation, to achieve the ultimate goal of practical saline water into freshwater conversion. At this juncture, it is imperative to review the recent opportunities and progresses of the PMD system. Here, the fundamental photothermal processes, strategies for efficient evaporator design, evaluation of various criteria for photothermal material incorporation with desired properties, discussions on desalination, water treatment, and energy generation applications are covered. Guidelines in material and system designs to further advance the PMD system that is highly promising in delivering portable water for both large-scale and decentralized systems are provided.