RESUMO
Superhydrophobic coating has a great application prospect in self-cleaning and oil-water separation but remains challenging for large-scale preparation of robust and weather-resistant superhydrophobic coatings via facile approaches. Herein, this work reports a scalable fabrication of weather-resistant superhydrophobic coating with multiscale rough coral reef-like structures by spraying the suspension containing superhydrophobic silica nanoparticles and industrial coating varnish on various substrates. The coral reef-like structures effectively improves the surface roughness and abrasion resistance. Rapid aging experiments (3000 h) and the outdoor building project application (3000 m2 ) show that the sprayed superhydrophobic coating exhibits excellent self-cleaning properties, weather resistance, and environmental adaptability. Moreover, the combined silica-coating varnish-polyurethane (CSCP) superhydrophobic sponge exhibits exceptional oil-water separation capabilities, selectively absorbing the oils from water up to 39 times of its own weight. Furthermore, the molecular dynamics (MD) simulation reveals that the combined effect of higher surface roughness, smaller diffusion coefficient of water molecules, and weaker electrostatic interactions between water and the surface jointly determines the superhydrophobicity of the prepared coating. This work deepens the understanding of the anti-wetting mechanism of superhydrophobic surfaces from the perspective of energetic and kinetic properties, thereby paving the way for the rational design of superhydrophobic materials and their large-scale applications.
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Bacterial adhesion and colonization on material surfaces pose a serious problem for healthcare-associated devices. Cationic amphiphilic polymer brushes are usually used as surface coatings in antibacterial materials to endow an interface with excellent bactericidal efficiency, but they are easily contaminated, which puts a great limitation on their application. Herein, novel antibacterial copolymer brush surfaces containing geminized cationic amphiphilic polymers (pAGC8) and thermoresponsive poly(N-isopropylacrylamide) polymers (pNIPAm) have been synthesized. Surface functionalization of polymer brushes was investigated by X-ray photoelectron spectroscopy, spectroscopic ellipsometry, atomic force microscopy, and water contact angle measurements. A proportion of AGC8 and NIPAm units in copolymer brushes has been adjusted to obtain a high-efficiency bactericidal surface with minimal interference to its self-cleaning property. The killing and releasing efficiency of the optimized surface simultaneously reached up to above 80% for both Staphylococcus aureus and Escherichia coli bacteria, and the bactericidal and self-cleaning abilities are still excellent even after three kill-release cycles. Such a novel copolymer brush system provides innovative guidance for the development of high-efficiency antibacterial materials in biomedical application.
Assuntos
Antibacterianos , Polímeros , Antibacterianos/química , Antibacterianos/farmacologia , Staphylococcus aureus/química , Escherichia coli/química , Polímeros/química , Polímeros/farmacologia , Espectroscopia Fotoeletrônica , Propriedades de SuperfícieRESUMO
Selective carbon capture from exhaust gas and biogas, which mainly involves the separation of CO2/N2 and CO2/CH4 mixtures, is of paramount importance for environmental and industrial requirements. Herein, we propose an interesting metal-organic framework-based nanotrap, namely ZnAtzCO3 (Atz- = 3-amino-1,2,4-triazolate, CO32- = carbonate), with a favorable ultramicroporous structure and electrostatic interactions that facilitate efficient capture of CO2. The structural composition and stability were verified by FTIR, TGA, and PXRD techniques. Particularly, ZnAtzCO3 demonstrated high CO2 capacity in a wide range of pressures, with values of 44.8 cm3/g at the typical CO2 fraction of the flue gas (15 kPa) and 56.0 cm3/g at the CO2 fraction of the biogas (50 kPa). Moreover, ultrahigh selectivities over CO2/N2 (15:85, v:v) and CO2/CH4 (50:50, v:v) of 3538 and 151 were achieved, respectively. Molecular simulations suggest that the carbon atom of CO2 can form strong electrostatic Cδ+···Î´-O-C interactions with four oxygen atoms in the carbonate ligands, while the oxygen atom of CO2 can interact with the hydrogen atoms in the triazolate ligands through Oδ-···Î´+H-C interactions, which makes ZnAtzCO3 an optimal nanotrap for CO2 fixation. Furthermore, breakthrough experiments confirmed excellent real-world separation toward CO2/N2 and CO2/CH4 mixtures on ZnAtzCO3, demonstrating its great potential for selective CO2 capture.
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Production of multicarbon (C2+ ) liquid fuels is a challenging task for electrocatalytic CO2 reduction, mainly limited by the stabilization of reaction intermediates and their subsequent C-C couplings. In this work, we report a unique catalyst, the coordinatively unsaturated Cu sites on amorphous CuTi alloy (a-CuTi@Cu) toward electrocatalytic CO2 reduction to multicarbon (C2-4 ) liquid fuels. Remarkably, the electrocatalyst yields ethanol, acetone, and n-butanol as major products with a total C2-4 faradaic efficiency of about 49 % at -0.8â V vs. reversible hydrogen electrode (RHE), which can be maintained for at least 3â months. Theoretical simulations and in situ characterization reveals that subsurface Ti atoms can increase the electron density of surface Cu sites and enhance the adsorption of *CO intermediate, which in turn reduces the energy barriers required for *CO dimerization and trimerization.
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Large pore sizes, high pore volumes, facile synthesis conditions, and high space-time yields are recognized as four crucial criteria in the fabrication of metal-organic frameworks (MOFs). However, these four objectives are rarely realized together. Herein, we have developed a simple and versatile method that employs 1,4-butanediamine (BTDM) as a template for rapidly fabricating four stable hierarchically porous MOFs (H-MOFs), including HKUST-1, ZIF-8, ZIF-67, and ZIF-90. The synthesis conditions are simple and facile at room temperature and ambient pressure, and the synthesis time can be shortened to 1 min. The resultant H-MOFs exhibit multimodal hierarchically porous structures with meso- and macropores interconnected with micropores, as well as high pore volumes (0.76 cm3 g-1). The maximum space-time yield for the hierarchically porous HKUST-1 reaches 7.4 × 104 kg m-3 d-1, at least one order of magnitude higher than previous reported yields. Notably, the additive BTDM not only facilitates crystal growth but also guides the formation of meso- and macropores. The synthesis route is highly versatile, as analogues (e.g., tetramethyl-1,3-diaminopropane and tetramethyldiaminomethane) can also be employed as templates to prepare diverse H-MOFs. Furthermore, the porosities of the H-MOFs are readily tuned by controlling the metal source, template amount and type of template. The as-synthesized H-MOFs act as adsorbents with significantly improved performances relative to those of microporous MOFs used for CH4 and CO2 gas storage. This strategy may aid in the large-scale industrial synthesis of desirable H-MOFs for gas storage.
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Recovering cobalt from waste batteries is crucial for resource recycling and environmental protection. Here, MOF-OH, a Zr-based MOF, was synthesized and merged into a polyacrylonitrile (PAN) matrix to create MOF-OH-PAN nanofibers (NFs). These NFs showed a high cobalt ion adsorption capacity of 33.1 mg/g, retaining over 90% of the capacity after six cycles. The adsorption mechanism involves Co(II) surface diffusion followed by strong bonding with functional groups. This technology enables efficient cobalt recovery from waste batteries, supporting reuse and reducing resource depletion and environmental pollution. The study provides insights into waste battery resource management, highlighting environmental and economic benefits and contributing to green resource recovery and circular economy initiatives.
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In this work, a novel metal-organic frameworks (MOFs)-based ion-imprinted polymer (MIIP) was prepared to remove Co(II) from simulated radioactive wastewater. The batch experiments indicated that the sorption was well described by the pseudo-second-order kinetic and Langmuir models, and it is monolayer chemisorption. The theoretical maximum sorption capacity was estimated to be 181.5 mgâg-1, which is by far the reported maximum value of Co(II) sorption by the imprinted materials. The MIIP presented an excellent selectivity for Co(II) in the presence of common monovalent and divalent metal ions, and the selectivity coefficients were 44.31, 33.19, 10.84, 27.71, 9.45, 16.25, and 7.60 to Li(I), K(I), Mg(II), Ca(II), Mn(II), Ba(II), and Cd(II), respectively. The sorption mechanism was explored by X-ray photoelectron spectroscopy (XPS) technology and density functional theory (DFT) calculations, suggesting that Co(II) was adsorbed by the MIIP via the chelation of 4-vinylpyridine (VP) ligands with Co(II), which was a spontaneous process, and the optimal coordination ratio of VP to Co(II) was 6. This work suggested that the MIIP has a high sorption capacity and excellent selectivity for Co(II), which is of great significance for the selective separation of Co-60 from radioactive wastewater.
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The effective removal of uranium from an aqueous solution is a highly valuable process for the environment and health. In this study, we developed a facile and rapid method to synthesize hierarchically porous Cu-BTC (RT-Cu-BTC) using a cooperative template strategy. The as-synthesized RT-Cu-BTC exhibited hierarchically porous structure and excellent thermostability, as revealed by X-ray powder diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. Compared with conventional metal-organic frameworks (MOFs) and zeolites, the obtained RT-Cu-BTC exhibited enhanced adsorption capacity (839.7 mg·g-1) and high removal efficiency (99.8%) in the capture of uranium (VI) from aqueous solutions. Furthermore, the conditions such as adsorbent dose, contact time, and temperature in adsorption of uranium (VI) by RT-Cu-BTC were investigated in detail. The thermodynamics data demonstrated the spontaneous and endothermic nature of the uranium (VI) adsorption process. The Langmuir isotherm and pseudo-second-order models could better reflect the adsorption process of uranium (VI) onto RT-Cu-BTC. In addition, the as-synthesized RT-Cu-BTC showed excellent stability in removing uranium (VI) from an aqueous solution. This work provides a facile and rapid approach for fabricating hierarchically porous MOFs to realize a highly efficient removal of uranium (VI) from aqueous systems.
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Hierarchically porous metal-organic frameworks (MOFs) have recently emerged as a novel crystalline hybrid material with tunable porosity. Many efforts have been made to develop hierarchically porous MOFs, yet their low-energy fabrication remains a challenge and the underlying mechanism is still unknown. In this study, the rapid fabrication of two hierarchically porous MOFs (Cu-BTC and ZIF-8) was carried out at room temperature and ambient pressure for 10 min using a novel surfactant as the template in a (Cu, Zn) hydroxy double salt (HDS) solution, where the (Cu, Zn) HDS accelerated the nucleation of crystals and the anionic surfactants served as templates to fabricate mesopores and macropores. The growth mechanism of hierarchically porous MOFs was analyzed via mesodynamics (MesoDyn) simulation, and then the synthetic mechanism of hierarchically porous MOFs at the molecular level was obtained. The as-synthesized hierarchically porous Cu-BTC showed a high uptake capacity of 646 mg g-1, which is about 25% higher as compared with microporous Cu-BTC (516 mg g-1) for the capture of toluene. This study provides a theoretical basis for the large-scale fabrication of hierarchically porous MOFs and offers a reference for the understanding of their synthetic mechanism.