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The green and environmentally friendly cardanol epoxy resin has a bright application prospect, but its insufficient thermal/mechanical properties seriously hinder its application. Adding nanoclay to polymer matrix is an effective method to enhance the thermal/mechanical properties of material, but the dispersion and compatibility of nanoclay in epoxy resin remain to be solved. In this work, active Girard's reagent clay (PG-clay) and non-active Girard's reagent clay (NG-clay) were prepared by using acethydrazide trimethylammonium chloride (Girard's reagent) as the modifier, and cardanol epoxy resin/G-clay nanocomposites were synthesized by the "clay slurry composite method". The results showed that both PG-clay and NG-clay were dispersed in the epoxy matrix in the form of random exfoliation/intercalation, which effectively improved the thermal/mechanical properties of the composites. Tg of the cardanol epoxy resin has raised from 19.8 °C to 38.1 °C (4 wt.% PG-clay). When the mass fraction of clay is 4%, the tensile strength of the non-reactive NG-clay increases by 128%, and the elongation at break also increases by 101%. Simultaneously, the active PG-clay can participate in the curing reaction of epoxy resin due to the amino group, forming a chemical bond between the clay layer and the resin matrix and establishing a strong interfacial force. The tensile strength of the composite is increased by 970%, and the elongation at break is also increased by 428%. This research demonstrates that the cardanol epoxy resin/G-clay nanocomposite stands as a highly promising candidate for bio-based epoxy resin materials.
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Surface-initiated iron(0)-mediated controlled radical polymerization (SI-Fe0CRP) with low toxicity and excellent biocompatibility is promising for the fabrication of biofunctional polymer coatings. However, the development of Fe(0)-based catalysts remains limited by the lower dissociation activity of the Fe(0) surface in comparison to Cu(0). Here, we found that, by simply polishing the Fe(0) plate surface with sandpaper, the poly(methacryloyloxy)ethyl trimethylammonium chloride brush growth rate has been increased significantly to 3.3 from 0.14 nm min-1 of the pristine Fe(0) plate. The excellent controllability of roughness-mediated SI-Fe0CRP can be demonstrated by customizing multicompartment brushes and triblock brushes. Furthermore, we found that the resulting polymer brush coatings exhibit remarkably low water adhesion (0.097 mN) and an outstanding drag reduction rate of 52% in water. This work provides a promising strategy for regulating the grafting rate of polymer brushes via SI-Fe0CRP for biocompatible marine drag reduction coatings.
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Imine-linked covalent organic frameworks (COFs) usually show high crystallinity and porosity, while vinyl-linked COFs have excellent semiconducting properties and stability. Therefore, achieving the advantages of imine- and vinyl-linkages in a single COF material is highly interesting but remains challenging. Herein, we demonstrate the fabrication of a layer-blocked COF (LB-COF) heterogeneous film that is composed of imine- and vinyl-linkages through two successive surface-initiated polycondensations. In brief, the bottom layer of imine-linked COF film was constructed on an amino-functionalized substrate via Schiff-base polycondensation, in which the unreacted aldehyde edges could be utilized for initiating aldol polycondensation to prepare the second layer of vinyl-linked COF film. The resultant LB-COF film displays excellent ordering due to the crystalline templating effect from the bottom imine-linked COF layer; meanwhile, the upper vinyl-linked COF layer could strongly enhance its stability and photocatalytic properties. The LB COF also presents superior performance in photocatalytic uranium extraction (320 mg g-1), which is higher than the imine-linked (35 mg g-1) and the vinyl-linked (295 mg g-1) counterpart. This study provides a novel surface-initiated strategy to synthesize layer-blocked COF heterogeneous films that combine the advantages of each building block.
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Surface-tethered poly(ionic liquid) brushes have attracted considerable attention in widespread fields, from bioengineering to marine antifouling. However, their applications have been constrained due to the poor polymerization efficiency and sophisticated operation process. In this work, we efficiently synthesized the poly(ionic liquid) brushes with unparalleled speed (up to 98 nm h-1) through Fe0-mediated surface-initiated atom transfer radical polymerization (Fe0 SI-ATRP) while consuming only microliter of monomer solution under ambient conditions. We also demonstrated that poly(ionic liquid) brushes with gradient thickness and wettability were easily accessible by regulating the distance between the opposite plates of Fe0 SI-ATRP. Moreover, the resultant poly(ionic liquid) brushes presented excellent antibacterial activities against Escherichia coli (99.2%) and Bacillus subtilis (88.1%) after 24 h and low attachment for proteins and marine algae (≤5%) for over 2 weeks. This research provided pathways to the facile and controllable fabrication of poly(ionic liquid) materials for marine antifouling applications.
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Sp2-carbon-conjugated covalent organic frameworks (sp2c-COFs) have emerged as promising platforms for phototo-chemical energy conversion due to their tailorable optoelectronic properties, in-plane π-conjugations, and robust structures. However, the development of sp2c-COFs in photocatalysis is still highly hindered by their limited linkage chemistry. Herein, we report a novel thiadiazole-bridged sp2c-COF (sp2c-COF-ST) synthesized by thiadiazole-mediated aldol-type polycondensation. The resultant sp2c-COF-ST demonstrates high chemical stability under strong acids and bases (12 M HCl or 12 M NaOH). The electro-deficient thiadiazole together with fully conjugated and planar skeleton endows sp2c-COF-ST with superior photoelectrochemical performance and charge-carrier separation and migration ability. As a result, when employed as a photocathode, sp2c-COF-ST exhibits a significant photocurrent up to â¼14.5 µA cm-2 at 0.3 V vs reversible hydrogen electrode (RHE) under visible-light irradiation (>420 nm), which is much higher than those analogous COFs with partial imine linkages (mix-COF-SNT â¼ 9.5 µA cm-2) and full imine linkages (imi-COF-SNNT â¼ 4.9 µA cm-2), emphasizing the importance of the structure-property relationships. Further temperature-dependent photoluminescence spectra and density functional theory calculations demonstrate that the sp2c-COF-ST has smaller exciton binding energy as well as effective mass in comparison to mix-COF-SNT and imi-COF-SNNT, which suggests that the sp2c-conjugated skeleton enhances the exciton dissociation and carrier migration under light irradiation. This work highlights the design and preparation of thiadiazole-bridged sp2c-COFs with promising photocatalytic performance.
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Surface-enhanced Raman scattering (SERS) spectroscopy is a powerful technology in trace analysis. However, the wide applications of SERS in practice are limited by the expensive substrate materials and the complicated preparation processes. Here we report a simple and economical galvanic-replacement-assisted synthesis route to prepare Ag nanoparticles on Cu(0) foil (nanoAg@Cu), which can be directly used as SERS substrate. The fabrication process is fast (ca. 10 min) and easily scaled up to centimeters or even larger. In addition, the morphology of the nanoAg@Cu (with Ag particles size from 30 nm to 160 nm) can be adjusted by various additives (e.g., amino-containing ligands). Finally, we show that the as-prepared nanoAg@Cu can be used for SERS characterization of two-dimensional polymers, and ca. 298 times relative enhancement of Raman intensity is achieved. This work offers a simple and economical strategy for the scalable fabrication of silver-based SERS substrate in thin film analysis.
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ConspectusThe surface-tethered polymer brush has become a powerful approach to tailoring the chemical and physical properties of surfaces and interfaces and revealed broad application prospects in widespread fields such as self-cleaning, surface lubrication, and antibiofouling. Access to these diverse functional polymer brushes is highly dependent on versatile and powerful surface-initiated controlled radical polymerization (SI-CRP) strategies. However, conventional SI-CRP typically requires oxygen exclusion, large amounts of catalysts and monomer solution, and a long reaction time, making it time-consuming and sophisticated. When using a two-plate system consisting of an initiator-bearing substrate and a metal plate, we and our collaborators introduced surface-initiated zerovalent metal-mediated controlled radical polymerization (SI-Mt0CRP). In the SI-Mt0CRP setup, a metal(0) plate (Cu, Fe, Zn, or Sn) is placed proximately to an initiator-functionalized substrate and forms a confined polymerization system which considerably simplifies the synthesis of a wide range of polymer brushes with high grafting densities over large areas (up to the meter scale).In comparison to classical SI-ATRP (catalyzed by metal salts), SI-Mt0CRP demonstrates oxygen tolerance, high controllability, good retention of chain-end functionality, and facile recyclability of the metal catalysts (i.e., metal foil/plate). Taking advantage of the confined geometry of the SI-Mt0CRP setup, polymer brushes with various conformations and architectures are easily accessible while consuming only microliter volumes of monomer solution and without complicated operations under ambient conditions. Owing to these attractive characteristics, SI-Mt0CRP has become a versatile technique for functionalizing materials for targeted applications, ranging from the areas of surface science to materials science and nanotechnology.In this Account, we summarize the recent advances of SI-Mt0CRP catalyzed by zerovalent metals (e.g., Cu, Fe, Zn, and Sn) and highlight the intrinsic advantages of the featured experimental setup, compared with the "classical" SI-CRP in which metal salt, powder, or wire is applied. We further discuss the synthetic features and proposed mechanism of SI-Mt0CRP while emphasizing the various external technologies' (including "on water" reaction, galvanic replacement, lithography, and capillary microfluidic) integrated polymerization systems. We also describe structural polymer brushes, including block copolymers, patterned and gradient structures, and arrayed and binary polymer brushes. Finally, we introduce the diverse polymer brushes that have been prepared using these techniques, with a focus on targeted and emerging applications. We anticipate that the discussion presented in this Account will promote a better understanding of the SI-Mt0CRP technique and advance the future development of practical surface brushing.
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Ice is omnipresent in our daily life and possesses intrinsic slipperiness as a result of the formation of a quasi-liquid layer. Thus, the functional surfaces inspired by ice show great prospects in widespread fields from surface lubrication to antifouling coatings. Herein, we report an ice-inspired polymeric slippery surface (II-PSS) constructed by a self-lubricating liquid layer and a densely surface-grafted polymer brush. The polymer brush layer could act as a homogeneous matrix to capture lubricant molecules via strong and dynamic dipole-dipole interactions to form a stable quasi-liquid layer that resembles the ice surface. The II-PSS can be easily fabricated on various solid substrates (e.g., silicon, glass, aluminum oxide, plastics, etc.) with excellent smoothness (roughness of â¼0.4 nm), optical transmittance (â¼94.5%), as well as repellence toward diverse liquids with different surface tensions (22.3-72.8 mN m-1), pH values (1-14), salinity, and organic pollutants. Further investigation shows that the II-PSS exhibits extremely low attachment for proteins and marine organisms (e.g., algae and mussels) for over one month. These results demonstrate a robust and promising strategy for high-performance antifouling coatings.
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Copper-based materials are very important for many application fields from marine industry to energy management and electronic devices. For most of these applications, the copper objects require long-term contact to a wet and salty environment, which leads to serious corrosion of copper. In this work, we report a thin graphdiyne layer directly grown on arbitrary shapes of copper objects at mild conditions, which could function as a protective coating for the copper substrates in artificial seawater with corrosion inhibition efficiency of â¼99.75%. To further improve the protective performance of the coating, the graphdiyne layer is fluorinated and followed by infusion with a fluorine-containing lubricant (i.e., perfluoropolyether). As a result, a slippery surface is obtained, which shows enhanced corrosion inhibition efficiency of â¼99.99% as well as excellent antibiofouling properties against microorganisms, such as protein and algae. Finally, the coatings are successfully applied in the protection of a commercial copper radiator from long-term attack of artificial seawater without disturbing its thermal conductivity. These results demonstrate the great potential of graphdiyne-based functional coatings for the protection of copper devices in aggressive environments.
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Surface anchored polymer brushes prepared by surface-initiated controlled radical polymerization (SI-CRP) have raised considerable interest in biomaterials and bioengineering. However, undesired residues of noxious transition metal catalysts critically restrain their widespread biomedical applications. Herein, we present a robust and biocompatible surface-initiated controlled radical polymerization catalyzed by a Sn(0) sheet (SI-Sn0CRP) under ambient conditions. Through this approach, microliter volumes of vinyl monomers with diverse functions (heterocyclic, ionic, hydrophilic, and hydrophobic) could be efficiently converted to homogeneous polymer brushes. The excellent controllability of SI-Sn0CRP strategy is further demonstrated by the exquisite fabrication of predetermined block and patterned polymer brushes through chain extension and photolithography, respectively. Additionally, in virtue of intrinsic biocompatibility of Sn, the resultant polymer brushes present transcendent affinity toward blood and cell, in marked contrast to those of copper-based approaches. This strategy could provide an avenue for the controllable fabrication of biocompatible polymer brushes toward biological applications.
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Materiales Biocompatibles , Polímeros , Polimerizacion , Polímeros/química , Cobre/química , IngenieríaRESUMEN
Here we present a facile and robust strategy, namely, galvanic-replacement-assisted surface-initiated Cu(0)-mediated atom transfer radical polymerization (gr-SI-Cu0ATRP, or gr-SI-Cu0CRP) for polymer brush engineering under ambient conditions. In gr-SI-Cu0ATRP, highly active and nanostructured Cu(0) surfaces are obtained by a simple galvanic replacement on zinc/aluminum surfaces in dilute Cu2+ solution. Polymer brush growth rate is extremely high (up to â¼904 nm in 30 min polymerization); meanwhile, both nano Cu(0) surfaces and Cu2+ solution can be reused multiple times without losing grafting efficiency. We also demonstrate that the gr-SI-Cu0ATRP is advantageous for polymer brush engineering on arbitrary substrates, including flexible (polyethylene terephthalate), curved (polycarbonate), and porous (anodic aluminum oxide), and endow the substrates with various functionalities, for example, anti-icing, antifogging, and ion selectivity.
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Óxido de Aluminio , Polímeros , Polimerizacion , Propiedades de SuperficieRESUMEN
Iron-mediated surface-initiated reversible deactivation radical polymerization (Fe0 SI-RDRP) is an appealing approach to produce robust polymer surfaces with low toxicity and biocompatibility, while its application has been limited so far due to the poor activity of iron-based catalysts. Herein, we show that the iron(0)-mediated surface-initiated atom transfer radical polymerization (Fe0 SI-ATRP) could be significantly enhanced by simply using seawater as reaction media. In comparison, there was no polymer brush formation in deionized water. This method could convert a range of monomers to well-defined polymer brushes with unparalleled speed (up to 31.5 nm min-1) and a minor amount of monomer consumption (µL). Moreover, the resultant polymer brush shows chain-end fidelity which could be exemplified by repetitive Fe0 SI-ATRP to obtain tetrablock brushes. Finally, we show the preparation of polymer-brush-gated ion-selective membranes by Fe0 SI-ATRP for osmotic energy conversion, which gives excellent power densities of 5.93 W m-2, outperforming the most reported as well as commercialized benchmark (5 W m-2).
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Hierro , Polímeros , Polimerizacion , Agua de Mar , Propiedades de SuperficieRESUMEN
Directional transportation and manipulation of liquid droplets, which are of great significance for science and technologies, are mainly dependent on special surface wettability. Inspired by the carnivorous nepenthes, we fabricate a paraffin infused hybrid porous hydroxyapatite nanowires/carbon nanofibers film (PIHPHCF). The inorganic hydroxyapatite nanowires (HAPNWs) firmly intertwine with the carbon nanofibers (CNTs) to form a three-dimensional porous network after the self-assembly process. On account of the CNTs' photothermal effect, the infused paraffin in PIHPHCF can transform from the solid state to a liquid state in response to near-infrared light irradiation (NIRLI, 808 nm), causing the wettability of the film to convert from hydrophobic to slippery. Through inducting variform mask layers, the slippery pathways melting from the lubricating paraffin are adjusted to different shapes such as 'S' and 'Y', where liquid droplets are able to be directionally transported. Additionally, potential application of the as-prepared patterned slippery film is explored as a microreactor and microfluidics device. Moreover, such a patterned slippery surface is successfully utilized to explore bubbles capture, manipulation and release under a warm-water environment. We anticipate that this work is poised to broaden the application of patterned slippery surfaces, as an example of which is liquid or bubble controllable transportation and manipulation.
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Inspired by biological surfaces, we designed a magnetic fiber trichome based on the surface properties of caterpillars and earthworms. The caterpillar-inspired fiber trichome possesses a cooperative superhydrophilic-superhydrophobic-slippery lubricant-infused porous surface with gradient wettability and shows excellent fog harvesting behavior due to the driving force of the gradient wettability fiber similar to caterpillar spines. The earthworm-inspired fiber trichome exhibits excellent friction reduction and antiwear properties under harsh oil-bathed friction conditions, and it moves rapidly in mud under magnetic stimulation because of the self-lubricating transfer film formed between friction contact surfaces. In addition, the earthworm-inspired fiber trichome also has continuous antifouling capacity in mud due to the self-releasing lubricating layer that can be replenished after being consumed under solid friction. Therefore, the caterpillar- and earthworm-inspired fiber trichomes extend the scope of potential applications, such as self-driven water collection, self-floating oil spill cleanup, reducing friction and wear resistance, high-efficiency antifouling, and transport of heavy loads, among others.
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The wide application of superhydrophobic membranes has been limited due to their complicated preparation technology and weak durability. Inspired by the mechanical flexibility of nanofibrous biomaterials, nanofibrils have been successfully generated from Kevlar, which is one of the strongest synthetic fibers, by appropriate hydrothermal treatment. In this study, a robust superhydrophobic PDMS/PVDF@KNFs membrane is prepared via a simple one-step process and subsequent curing without combination with inorganic fillers. The as-prepared PDMS/PVDF@KNFs membrane not only shows efficient oil/water separation ability and oil absorption capacity but also has excellent superhydrophobicity stability after deformation. The resultant membrane shows stretchability, flexibility and flame retardance because of the reinforcing effect and the excellent flame retardancy of Kevlar. We believe that this simple fabrication of PDMS/PVDF@KNFs has promising applications in filtering membranes and wearable devices.