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The role of tannins (TA), a well-known abundant and ecologically friendly chelating ligand, in metal capture has long been studied. Different kinds of TA-containing adsorbents are synthesized for uranium capture, while most adsorbents suffer from unfavorable adsorption kinetics. Herein, the design and preparation of a TA-containing 2D crosslinked network adsorbent (TANP) is reported. The ≈1.8-nanometer-thick TANP films curl up into micrometer-scale pores, which contribute to fast mass transfer and full exposure of active sites. The coordination environment of uranyl (UO2 2+) ions is explored by integrated analysis of U L3-edge XANES and EXAFS. Density functional theory calculations indicate the energetically favorable UO2 2+ binding. Consequently, TANP with excellent adsorption kinetics presents a high uranium capture capacity (14.62 mg-U g-Ads-1) and a high adsorption rate (0.97 mg g-1 day-1) together with excellent selectivity and biofouling resistance. Life cycle assessment and cost analysis demonstrate that TANP has tremendous potential for application in industrial-scale uranium extraction from seawater.
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Two-dimensional polymers (2DPs) and their layer-stacked 2D covalent organic frameworks (2D COFs) membranes hold great potential for harvesting sustainable osmotic energy. The nascent research has yet to simultaneously achieve high ionic flux and selectivity, primarily due to inefficient ion transport dynamics. This is directly related to ultrasmall pore size (<3â nm), much smaller than the duple Debye length in the diluted electrolyte (6-20â nm), as well as low charge density (<4.5â mC m-2). Here, we introduce a π-conjugated viologen-based 2DP (V2DP) membrane possessing a large pore size of 4.5â nm, strategically enhancing the overlapping of the electric double layer, coupled with an exceptional positive surface charge density (~6â mC m-2). These characteristics enable the membrane to facilitate high anion flux while maintaining ideal selectivity. Notably, V2DP membranes realize an impressive current density of 5.5×103â A m-2, surpassing benchmarks set by previously reported nanofluidic membranes. In the practical application scenario involving the mixing of artificial seawater and river water, the V2DP membranes exhibit a considerable ion transference number of 0.70 towards Cl-, contributing to an outstanding power density of ~55â W m-2. Theoretical calculations reveal the important role of the large quantity of anion transport sites, which act as binding sites evenly located in the positively charged N-containing pyridine rings. These binding sites enable kinematic coupling and decoupling between anions and the V2DP skeleton, establishing a continuous Cl- ion transport pathway. This work demonstrates the great promise of large-area ultrathin 2DP membranes featuring highly organized charged ion transport networks when applied for osmotic energy conversion.
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Polymer single crystals are used as templates to synthesize polymer brushes, known as the "polymer-single-crystal-assisted-grafting-to" (PSCAGT) approach. Polymer brushes with controlled grafting densities and spatial tethering locations are demonstrated. Previous works focused on solution crystallization, which involves large amounts of organic solvent, and the grafting density can only be tuned by varying crystallization temperatures. In this work, thin film crystallization is utilized to fabricate 2D polymer crystals on flat surfaces. Subsequent chemical tethering leads to polymer brushes that retain the original morphology of the crystals with high fidelity. Furthermore, it is shown that the grafting density of the polymer brushes fabricated using this method depends on the chain end distribution on the top/bottom surfaces of the crystal, which can be facilely controlled by annealing the crystals at various nonsolvent media. This work broadens the scope of the PSCAGT method and provides a new route to achieve polymer brushes with controlled structures.
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Polímeros , Polímeros/química , Cristalização , Solventes , Propriedades de Superfície , TemperaturaRESUMO
Selective preparation of two-dimensional polymers (2DPs) and supramolecular polymers (2DSPs) with defined thickness is crucially important for controlling and maximizing their functions, yet it has remained as a synthetic challenge. In the past decade, several approaches have been developed to allow selective preparation of discrete monolayer 2DPs and 2DSPs. Recently, crystal exfoliation and self-assembly strategies have been employed to successfully prepare bilayer 2DP and 2DSP, which represent the first step towards the controlled "growth" of 2D polymers from the thinnest monolayers to thicker few-layers along the third dimension. This Concept review discusses the concept of accurate synthesis of 2D polymers with defined layers. Advances in this research area will pave the way to rational synthetic strategies for 2D polymers with controlled thickness.
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Polímeros , Polímeros/químicaRESUMO
Covalent organic frameworks (COFs) are molecule-based 2D and 3D materials that possess a wide range of mechanical and electronic properties. We have performed a joint experimental and theoretical study of the electronic structure of boroxine-linked COFs grown under ultrahigh vacuum conditions and characterized using scanning tunneling spectroscopy on Au(111) and hBN/Cu(111) substrates. Our results show that a single hBN layer electronically decouples the COF from the metallic substrate, thus suppressing substrate-induced broadening and revealing new features in the COF electronic local density of states (LDOS). The resulting sharpening of LDOS features allows us to experimentally determine the COF band gap, bandwidths, and the electronic hopping amplitude between adjacent COF bridge sites. These experimental parameters are consistent with the results of first-principles theoretical predictions.
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In the past few decades, enormous efforts have been made to synthesize covalent polymer nano/microstructured materials with specific morphologies, due to the relationship between their structures and functions. Up to now, the formation of most of these structures often requires either templates or preorganization in order to construct a specific structure before, and then the subsequent removal of previous templates to form a desired structure, on account of the lack of "self-error-correcting" properties of reversible interactions in polymers. The above processes are time-consuming and tedious. A template-free, self-assembled strategy as a "bottom-up" route to fabricate well-defined nano/microstructures remains a challenge. Herein, we introduce the recent progress in template-free, self-assembled nano/microstructures formed by covalent two-dimensional (2D) polymers, such as polymer capsules, polymer films, polymer tubes and polymer rings.
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Despite the recent progress in the synthesis of crystalline boronate ester covalent organic frameworks (BECOFs) in powder and thin-film through solvothermal method and on-solid-surface synthesis, respectively, their applications in electronics, remain less explored due to the challenges in thin-film processability and device integration associated with the control of film thickness, layer orientation, stability and crystallinity. Moreover, although the crystalline domain sizes of the powder samples can reach micrometer scale (up to ≈1.5â µm), the reported thin-film samples have so far rather small crystalline domains up to 100â nm. Here we demonstrate a general and efficient synthesis of crystalline two-dimensional (2D) BECOF films composed of porphyrin macrocycles and phenyl or naphthyl linkers (named as 2D BECOF-PP or 2D BECOF-PN) by employing a surfactant-monolayer-assisted interfacial synthesis (SMAIS) on the water surface. The achieved 2D BECOF-PP is featured as free-standing thin film with large single-crystalline domains up to ≈60â µm2 and tunable thickness from 6 to 16â nm. A hybrid memory device composed of 2D BECOF-PP film on silicon nanowire-based field-effect transistor is demonstrated as a bio-inspired system to mimic neuronal synapses, displaying a learning-erasing-forgetting memory process.
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Two-dimensional polymers (2DP) are a new class of materials that consist of a monolayer of ordered molecular building blocks, which have been covalently linked. One of these monomers was self-assembled on a flat muscovite mica scaffold and subsequently the organic layer was polymerized. The resulting flat and stable 2DP layer was used as a template for protein crystallization. Crystals of insulin were epitaxially grown on the template, whereas insulin crystals grown on clean muscovite mica had a random orientation. The template was selective, considering that no epitaxially ordered crystals formed of hen egg white lysozyme, bovine serum albumin, or talin.
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Established less than a decade ago, the fascinating field of two-dimensional (2D) soft materials is advancing continuously towards widespread recognition. After demonstrating the feasibility of obtaining nano-thin supramolecular sheets and morphologically related tubular objects, considerable efforts are being undertaken to explore the functional potential of soft nanosheets. Self-assembly is a major tool for the controlled formation of nanometre-sized 2D objects. In this account, we share our current understanding of the structural requirements to direct the self-assembly of water-soluble, negatively charged oligomers in 2D. The discussion covers some promising areas of utilization such as the reporting of weak mechanical perturbations, the assembly of light-harvesting antennae, the transfer of excitation energy and the polymerization of pre-organized assemblies. The systems presented in this work illustrate the potential of 2D supramolecular materials as complementary systems to their covalent counterparts.
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Two-dimensional polymers comprise a novel class of macromolecules with promising mechanical and chemical properties that have recently become accessible under mild synthetic conditions. As nanometer-sized holes and defects are likely to influence these materials' properties, there is a need for analytical methods to spatially and chemically characterize them down to the nanoscale. In this article, we compare tip-enhanced Raman spectroscopy to common methods in nanoanalysis for the investigation of defect sites in molecularly thin 2D-polymer sheets and briefly present measures to meet the challenges arising from tip-induced degradation processes.
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Weaving is an old technique producing fabric materials by interlocking yarns, which we appreciate every day by wearing textiles. The splendid mechanical features of these macroscopic interwoven structures such as stability, flexibility, and shape adaptability raised the question whether or not such properties might also be observed on a molecular level. In this article, molecular analogues to textiles are discussed and strategies to molecular weaves are presented. While there are impressive structural similarities between the macroscopic and the molecular world, molecular textiles consisting of interwoven linear polymers remain a challenge. The scope of the article ranges from discrete superstructures like Solomon knots, over deoxyribonucleic acid (DNA) based nanoscale patterns and interwoven 2D sheets of coordination polymers, to weaving strategies interlinking small organic precursors.
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2D polymer sheets containing azobenzene are successfully prepared by a facile strategy of "2D self-assembly polymerization (2DSP)" via free radical polymerization in solution. A bola amphiphile containing azobenzene as a novel monomer is designed and synthesized. The results indicate that single-layer covalent pseudo-2D polymers on a micrometer scale are obtained after polymerization with vinyl monomers. Moreover, the 2D polymer sheets are highly sensitive to UV light due to incorporation of azobenzene groups into the polymer. Upon alternative irradiation with UV and visible light, the morphological transformation between sheets and rolled-up nanotubes can be achieved based on the reversible trans-to-cis photoisomerization of azobenzene units in the 2D polymer sheets.
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Compostos Azo/química , Luz , Polímeros/química , Raios Ultravioleta , Radicais Livres/química , Guanidinas/química , Isomerismo , Maleatos/química , Microscopia de Força Atômica , Nanotubos/química , Polimerização , Poliestirenos/química , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
A facile method has been developed for synthesizing polymer nanocapsules and thin films using multiple in-plane stitching of monomers by the formation of reversible disulfide linkages. Owing to the reversibility of the disulfide linkages, the nanostructured materials readily transform their structures in response to environmental changes at room temperature. For example, in reducing environments, the polymer nanocapsules release loaded cargo molecules. Moreover, reversible morphological transformations between these structures can be achieved by simple solvent exchanges. This work is a novel approach for the formation of robust nano/microstructured materials that dynamically respond to environmental stimuli.
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Dissulfetos/química , Nanocápsulas/química , Polímeros/síntese química , Termodinâmica , Conformação Molecular , Tamanho da Partícula , Polímeros/química , Propriedades de SuperfícieRESUMO
Blue energy between seawater and river water is attracting increasing interest, as one of the sustainable and renewable energy resources that can be harvested from water. Within the reverse electrodialysis applied in blue energy conversion, novel membranes with nanoscale confinement that function as selective ion transport mediums are currently in high demand for realizing higher power density. The primary challenge lies in constructing well-defined nanochannels that allow for low-energy barrier transport. This work proposes a concept for nanofluidic channels with a simultaneous dual electrostatic effect that can enhance both ion selectivity and flux. To actualize this, this work has synthesized propidium iodide-based two-dimensional polymer (PI-2DP) membranes possessing both skeleton charge and intrinsic space charge, which are spatially aligned along the ion transport pathway. The dual charge design of PI-2DP significantly enhances the electrostatic interaction between the translocating anions and the cationic polymer framework, and a high anion selectivity coefficient (≈0.8) is reached. When mixing standard artificial seawater and river water, this work achieves a considerable power density of 48.4 W m-2, outperforming most state-of-the-art nanofluidic membranes. Moreover, when applied between the Mediterranean Sea and the Elbe River, an output power density of 42.2 W m-2 is achieved by the PI-2DP. This nanofluidic membrane design with dual-layer charges will inspire more innovative development of ion-selective channels for blue energy conversion that will contribute to global energy consumption.
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Nociceptor is an important receptor in the organism's sensory system; it can perceive harmful stimuli and send signals to the brain in order to protect the body in time. The injury degree of nociceptor can be divided into three stages: self-healing injury, treatable injury, and permanent injury. However, the current studies on nociceptor simulation are limited to the self-healing stage due to the limitation of the untunable resistance switching behavior of memristors. In this study, we constructed Al/2DPTPAK+TAPB/Ag memristor arrays with adjustable memory behaviors to emulate the nociceptor of biological neural network of all three stages. For this purpose, a PDMS/AgNWs/ITO/PET pressure sensor was assembled to mimic the tactile perception of the skin. The memristor arrays can not only simulate all the response of nociceptor, i.e., the threshold, relaxation, no adaptation, and sensitization with the self-healing injury, but can also simulate the treatable injury and the permanent injury. These behaviors are both demonstrated with a single memristor and in the form of pattern mapping of the memristor array.
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Tato , Tato/fisiologia , Polímeros/química , Humanos , Dimetilpolisiloxanos/químicaRESUMO
Fluorine-containing 2D polymer (F-2DP) film is a desired system to regulate the charge transport in organic electronics but rather rarely reports due to the limited fluorine-containing building blocks and difficulties in synthesis. Herein, a novel polar molecule with antiparallel columnar stacking is synthesized and further embedded into an F-2DP system to control over the crystallinity of F-2DP film through self-complementary π-electronic forces. The donor-accepter-accepter'-donor' (D-A-A'-D') structure regulates the charge transportation efficiently, inducing multilevel memory behavior through stepwise charge capture and transfer processes. Thus, the device exhibits ternary memory behavior with low threshold voltage (Vth1 of 1.1 V, Vth2 of 2.0 V), clearly distinguishable resistance states (1:102:104) and ternary yield (83%). Furthermore, the stepwise formation of the charge complex endows the device with a wider range to regulate the conductive state, which allows its application in brain-inspired neuromorphic computing. Modified National Institute of Standards and Technology recognition can reach an accuracy of 86%, showing great potential in neuromorphic computing applications in the post-Moore era.
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Large-scale growth of highly crystalline single layer 2D polymers (SL-2DPs) and their subsequent integration into memristors is key to advancing the development of high-density data storage devices. However, leakage problems resulting from the porous structure of 2DPs continue to make such advances extremely challenging. Herein, we overcome this issue by incorporating long alkoxy chains into key molecular building blocks to obtain a highly crystalline 2DP, as visualized by scanning tunneling microscopy, and prevent metal permeation in the subsequent device fabrication process. SL-2DP memristors constructed via direct evaporation of the top electrodes exhibit low variability (σVset = 0.14) due to the single-monomer-thick feature together with the high regular structure and coordination ability which minimizes the stochastic spatial distribution of conductive filaments (CFs) in both vertical and lateral dimensions. The variability is further decreased to 0.04 by confining the formation and fracture of CFs to the interface through the utilization of bilayer junctions. Using peak force tunneling atomic force microscopy, the nanometer scalability (< 50 nm2 ) and low power consumption of these molecular memristor devices are demonstrated.
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Since the discovery of single-layer graphene in 2004, the family of 2D inorganic nanosheets is considered as ideal membrane materials due to their ultrathin atomic thickness and fascinating physicochemical properties. However, the intrinsically nonporous feature of 2D inorganic nanosheets hinders their potential to achieve a higher flux to some extent. Recently, 2D polymer nanosheets, originated from the regular and periodic covalent connection of the building units in 2D plane, have emerged as promising candidates for preparing ultrafast and highly selective membranes owing to their inherently tunable and ordered pore structure, light weight, and high specific surface. In this review, the synthetic methodologies (including top-down and bottom-up methods) of 2D polymer nanosheets are first introduced, followed by the summary of 2D polymer nanosheets-based membrane fabrication as well as membrane applications in the fields of gas separation, water purification, organic solvent separation, and ion exchange/transport in fuel cells and lithium-sulfur batteries. Finally, based on their current achievements, the authors' personal insights are put forward into the existing challenges and future research directions of 2D polymer nanosheets for membrane separation. The authors believe this comprehensive review on 2D polymer nanosheets-based membrane separation will definitely inspire more studies in this field.
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Organic electrode materials are of long-standing interest for next-generation sustainable lithium-ion batteries (LIBs). As a promising cathode candidate, imide compounds have attracted extensive attention due to their low cost, high theoretical capacity, high working voltage, and fast redox reaction. However, the redox active site utilization of imide electrodes remains challenging for them to fulfill their potential applications. Herein, the synthesis of a highly stable, crystalline 2D polyarylimide (2D-PAI) integrated with carbon nanotube (CNT) is demonstrated for the use as cathode material in LIBs. The synthesized polyarylimide hybrid (2D-PAI@CNT) is featured with abundant π-conjugated redox-active naphthalene diimide units, a robust cyclic imide linkage, high surface area, and well-defined accessible pores, which render the efficient utilization of redox active sites (82.9%), excellent structural stability, and fast ion diffusion. As a consequence, high rate capability and ultrastable cycle stability (100% capacity retention after 8000 cycles) are achieved in the 2D-PAI@CNT cathode, which far exceeds the state-of-the-art polyimide electrodes. This work may inspire the development of novel organic electrodes for sustainable and durable rechargeable batteries.
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Single layers of covalently linked organic materials in the form of two-dimensional (2D) polymers constitute structures complementary to inorganic 2D materials. The electronic properties of 2D polymers may be manipulated through a deliberate choice of the organic precursors. Here we address the changes in electronic structure-from precursor molecule to oligomer-by scanning tunneling spectroscopy and ultraviolet photoelectron spectroscopy. For this purpose, we introduce the polymerization reaction of 1,3,5-tris(4-carboxyphenyl)benzene via decarboxylation on Cu(111), which is thoroughly characterized by scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. We present a comprehensive study of a contamination-free on-surface coupling scheme and study how dehydrogenation, decarboxylation, and polymerization affect the electronic structure on the molecular level.