Separation Efficiency Research Articles

Metal-Organic Framework Templated Z-Scheme ZnIn2S4/Bi2S3 Hierarchical Heterojunction for Photocatalytic H2O2 Production from Wastewater.

Metal-organic framework derived materials received a lot of attention due to their significant benefits in photocatalytic reactions. In this work, a Z-scheme ZnIn2S4/Bi2S3 hierarchical heterojunction is first developed by a one-pot method using CAU-17 as a template. The specific preparation method endows an intimate interface contact between these two monomers, and CAU-17-derived Bi2S3 possesses a high surface area and porosity, resulting in an efficient charge separation and O2 capture. Thus, for photocatalytic H2O2 production from the O2 reduction reaction, the ZnIn2S4/Bi2S3 heterojunction can achieve an H2O2 yield of 995µmolL-1 in pure water and ambient air under visible light, 4.5 and 4 times that of ZnIn2S4 and Bi2S3, respectively. In addition, in tetracycline solution, ZnIn2S4/Bi2S3 can degrade tetracycline with a degradation rate of 95% by photocatalysis, and at the same time, a final H2O2 production yield of 1223µmolL-1 is reached. Similarly, high yields of H2O2 are also obtained from wastewater containing o-nitrophenol, acid golden yellow, or acid red, and these pollutants are effectively degraded. This work reveals the potential of metal-organic framework-derived materials in photocatalysis, as well as provides insights into H2O2 green synthesis and wastewater treatment.

New strategy for structure rearrangement of thin-film composite (TFC) polyamide (PA) membranes and offering potential use in both aqueous and organic solvents

The purity of sodium hexafluorophosphate (NaPF6) is crucial for the preparation of electrolytes in manufacturing. We propose a simple process in order to induce membrane structure rearrangement process (SRP) by activating thin-film composite (TFC) membranes with polyamide (PA) structure and explore their potential green recycling application in concentrating sodium-ion batteries (SIBs) electrolyte. The method utilizes a solution containing polar aprotic solvent as the soaking and activating solution to swell and disintegrate the loosely cross-linked PA layer, and a non-solvent solidification solution complete the SRP, enhancing the permeability of the PA layer while maintaining high rejection rates for divalent ions. Subsequently, during the further treatment of the membrane surface in structure rearrangement, tert-butanol (TBA) is introduced into the aqueous solution to reconstruct the surface PA layer, further improving the permeability. The optimal D8010T10 achieved a permeation flux of 24.2 L m−2 h−1·bar−1, with rejection rates for sodium sulfate (Na2SO4), magnesium chloride (MgCl2), and magnesium sulfate (MgSO4) reaching 94.7 %, 98.4 %, and 99.1 % respectively. And the mechanism of SRP with different solvent is analyzed and explained through dissipative particle dynamics (DPD) simulations. This study provides a commercially viable approach for manufacturing high-performance membranes. The D8010T10 membrane achieves more than 90 % separation efficiency for sodium hexafluorophosphate (NaPF6) dissolved in different solvents, providing a potential solution for the concentration and recovery of NaPF6 in lab-scale, verified its potential use in the organic solvent nanofiltration (OSN) and a path way for waste membrane recycling and degrading use in the industry.

In Situ Construction of CuTCPP/Bi4O5Br2 Hybrids for Improved Photocatalytic CO2 and Cr(VI) Reduction.

Global warming and heavy metal pollution pose tremendous challenges to human development, and photocatalysis is considered to be an effective strategy to solve these problems. Herein, copper(II) tetra (4-carboxyphenyl) porphyrin (CuTCPP) molecules were successfully in situ loaded onto Bi4O5Br2 by a hydrothermal approach. A series of experimental results show that the light absorption capacity and photogenerated carrier separation efficiency were synchronously enhanced after the construction of CuTCPP/Bi4O5Br2 composites. Hence, the as-prepared composites possess significantly improved photocatalytic ability for both CO2 and Cr(VI) reduction. Specifically, CuTCPP/Bi4O5Br2-2 achieves a CO generation rate of 17.14 μmol g-1 under 5 h irradiation, which is twice as high as that of Bi4O5Br2 (8.57 μmol g-1). Besides, the optimized CuTCPP/Bi4O5Br2-2 also exhibits a removal rate of 61.87% for Cr(VI) within 100 min under irradiation. Furthermore, the mechanism of CO2 and Cr(VI) photoreduction was explored by in situ Fourier transform infrared spectroscopy and capture experiments, respectively. This work can be a reference toward the construction of photocatalysts with high activity for solar energy conversion.

Isomeric Porous Cu(I) Triazolate Frameworks Showing Periodic and Aperiodic Flexibility for Efficient CO Separation.

Guest-induced (crystal-to-crystal) transformation, i.e., periodic flexibility, is a typical feature of molecule-based crystalline porous materials, but its role for adsorptive separation is controversial. On the other hand, aperiodic flexibility is rarely studied. This work reports a pair of isomeric Cu(I) triazolate frameworks, namely, α-[Cu(fetz)] (MAF-2Fa) and β-[Cu(fetz)] (MAF-2Fb), which show typical periodic and aperiodic flexibility for CO chemical adsorption, respectively. Quantitative mixture breakthrough experiments show that, while MAF-2Fa exhibits high adsorption capacity at high pressures but negligible adsorption below the threshold pressure and with leakage concentrations of 3-8%, MAF-2Fb exhibits relatively low adsorption capacity at high pressures but no leakage (residual CO concentration <1 ppb). Tandem connection of MAF-2Fa and MAF-2Fb can combine their advantages of high CO adsorption capacities at high and low pressures, respectively. MAF-2Fa and MAF-2Fb can both keep the separation performances unchanged at high relative humidities, but only MAF-2Fb shows a unique coadsorption behavior at a relative humidity of 82%, which can be used to improve purification performances.

Direct Affinity Ligand Immobilization onto Bare Iron Oxide Nanoparticles Enables Efficient Magnetic Separation of Antibodies.

Magnetic separation is a promising alternative to chromatography for enhancing the downstream processing (DSP) of monoclonal antibodies (mAbs). However, there is a lack of efficient magnetic particles for successful application. Aiming to fill this gap, we demonstrate the suitability of bare iron oxide nanoparticles (BION) with physical site-directed immobilization of an engineered Protein A affinity ligand (rSpA) as an innovative magnetic material. The rSpA ligand contains a short peptide tag that enables the direct and stable immobilization onto the uncoated BION surface without commonly required laborious particle activation. The resulting BION@rSpA have beneficial characteristics outperforming conventional Protein A-functionalized magnetic particles: a simple, fast, low-cost synthesis, a particle size in the nanometer range with a large effective specific surface area enabling large immunoglobulin G (IgG) binding capacity, and a high magnetophoretic velocity advantageous for fast processing. We further show rapid interactions of IgG with the easily accessible rSpA ligands. The binding of IgG to BION@rSpA is thereby highly selective and not impeded by impurity molecules in perfusion cell culture supernatant. Regarding the subsequent acidic IgG elution from BION@rSpA@IgG, we observed a hampering pH increase caused by the protonation of large iron oxide surfaces after concentrating the particles in 100 mM sodium acetate buffer. However, the pH can be stabilized by adding 50 mM glycine to the elution buffer, resulting in recoveries above 85% even at high particle concentrations. Our work shows that BION@rSpA enable efficient magnetic mAb separation and could help to overcome emerging bottlenecks in DSP.

Magnetic separation, sunlight-driven photocatalytic activity, and antibacterial studies of Sm-doped Co0.33Mg0.33Ni0.33Fe2O4 nanoparticles.

Magnetic nanoparticles have emerged as a promising tool for wastewater treatment due to their unique properties. In this regard, Co0.33Mg0.33Ni0.33SmxFe2-xO4 (0.00 x 0.08) nanoparticles were prepared to examine their magnetic separation efficiency (MSE), photocatalytic, antibacterial, and antibiofilm performances. Pure nanoparticles, having the highest saturation magnetization (Ms = 31.87emu/g), exhibit the highest MSE, where 95.6% of nanoparticles were separated after 20min of applying a magnetic field of 150 mT. The catalytic performance of the prepared samples is examined by the photodegradation of rhodamine B (RhB) dye exposed to direct sunlight radiation. Improved photocatalytic activity is exhibited by Co0.33Mg0.33Ni0.33Sm0.04Fe1.96O4 nanoparticles, labeled as Sm0.04, where the rate of the degradation reaction is enhanced by 4.1 times compared to pure nanoparticles. Rising the pH and reaction temperature improves the rate of the photodegradation reaction of RhB. The incorporation of 15 wt% reduced graphene oxide (rGO) with Sm0.04 enhanced the rate of the reaction by 1.7 and 2.4 times compared with pure Sm0.04 sample and rGO, respectively. The antibacterial and antibiofilm activities against Escherichia coli, Leclercia adecarboxylata, Staphylococcus aureus, and Enterococcus faecium are assessed by the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC) broth microdilution, the agar well diffusion, the time-kill assays, the biofilm formation, and destruction assays. The bacteria used in these assessments are isolated from wastewater. The nanoparticles exhibit a bacteriostatic activity, with a better effect against the Gram-positive isolates. Co0.33Mg0.33Ni0.33SmxFe2O4 (x = 0.00) nanoparticles have the best effect. The effect is exerted after 2-3h of incubation. Gram-positive biofilms are more sensitive to nanoparticles.

Quantitative analysis of therapeutic peptides by CZE using multiple sample injection in hydrodynamically closed separation system.

Therapeutic peptides have emerged as an innovative and promising class of therapeutic compounds in modern medicine. Synthetic peptide analogs triptorelin and lanreotide are known for their pronounced clinical versatility and potency. In this study, we present the development and validation of novel methods based on capillary zone electrophoresis performed in hydrodynamically closed system (HCS) and paired with ultraviolet detection and repeated injection sample introduction. To the best of our knowledge, we developed the first capillary electrophoresis-based method for the determination of lanreotide, and concurrently, the first HCS method for the determination of triptorelin. Maximal separation efficiency and signal intensity were achieved using background electrolytes composed of 50mM formic acid with the addition of 0.05% (v/v) methyl-hydroxyethyl cellulose. The proposed methods exhibit favorable performance characteristics, namely, calibration curve (r2 exceeding 0.99), low limits of detection (0.25µg/mL in a water matrix and 0.5µg/mL in synthetic urine), acceptable precision (relative standard deviation ranging from 2.2% to 9.6% for intraday repeatability and between 5.2% and 14.9% for interday reproducibility), and accuracy (relative errors falling within the 91.1%-107.8% range). The method for triptorelin determination was then used for its quantification in a commercially available drug dosage form (powder for injection) and in spiked synthetic urine samples. The developed methods were also evaluated according to the novel blue applicability grade index, revealing their superior applicability. The results collectively point out the potential of the proposed methods for both quality control and clinical investigations.

Balancing the Kinetic and Thermodynamic Synergetic Effect of Doped Carbon Molecular Sieves for Selective Separation of C2H4/C2H6.

Selective separation of ethylene and ethane (C2H4/C2H6) is a formidable challenge due to their close molecular size and boiling point. Compared to industry-used cryogenic distillation, adsorption separation would offer a more energy-efficient solution when an efficient adsorbent is available. Herein, a class of C2H4/C2H6 separation adsorbents, doped carbon molecular sieves (d-CMSs) is reported which are prepared from the polymerization and subsequent carbonization of resorcinol, m-phenylenediamine, and formaldehyde in ethanol solution. The study demonstrated that the polymer precursor themselves can be a versatile platform for modifying the pore structure and surface functional groups of their derived d-CMSs. The high proportion of pores centered at 3.5Å in d-CMSs contributes significantly to achieving a superior kinetic selectivity of 205 for C2H4/C2H6 separation. The generated pyrrolic-N and pyridinic-N functional sites in d-CMSs contribute to a remarkable elevation of Henry selectivity to 135 due to the enhancement of the surface polarity in d-CMSs. By balancing the synergistic effects of kinetics and thermodynamics, d-CMSs achieve efficient separation of C2H4/C2H6. Polymer-grade C2H4 of 99.71% purity can be achieved with 75% recovery using the devised d-CMSs as reflected in a two-bed vacuum swing adsorption simulation.

Asymmetric Wettability Janus Mesh via Electrostatic Printing for Selective Oil-Water and Emulsion Separation.

Janus mesh with two-sided asymmetric wettability shows high potential for selective oil-water and emulsion separation. However, it remains a challenge to construct Janus mesh structures with good stability and extremely asymmetric wettability. Herein, a novel Janus mesh with asymmetric wettability was structured by two different precursors, polydimethylsiloxane/zinc oxide (PDMS/ZnO) and zinc oxide-polyacrylonitrile/N,N-dimethylformamide (ZnO-PAN/DMF), by electrostatic printing, including electrostatic air spraying and electrostatic spinning. The prepared Janus mesh has special micro-nanostructures on two sides, including PDMS@ZnO and ZnO@PAN. On the basis of gravity, when the placement direction is changed, Janus mesh can effectively separate oil-water mixtures of different densities and surfactant-stabilized oil-water emulsions. Meanwhile, the obtained Janus mesh exhibited good separation efficiency (>96.3%) for various oil-water mixtures, and the flux was up to 2621 ± 30 L m-2 h-1. The Janus mesh was cycled 20 times with no weakening in separation efficiency, indicating satisfactory cycling stability. The Janus mesh displayed good stability under harsh conditions (acidic, alkaline, and high temperature). The Janus mesh can realize low energy input and long-lasting oil-water separation, which has widespread application prospects in intelligent oil-water separation. This top-down electrostatic printing strategy provides a way to construct Janus interface materials with practical applications.

Efficient Xylene Isomer Separation: Accelerated Screening with Active Learning and Molecular Simulation

Efficient Xylene Isomer Separation: Accelerated Screening with Active Learning and Molecular Simulation

Visible-light harvesting SrTiO3 solid solutions for photocatalytic hydrogen evolution from water.

The fabrication of solid solutions represents a compelling approach to modulating the physicochemical properties of materials. In this study, we achieved the successful synthesis of solid solutions comprising SrTiO3 and SrTaO2N (denoted as (SrTiO3)1-x-(SrTaO2N)x, 0 ≤ x ≤ 1) using the magnesium powder-assisted nitridation method. The absorption edge of (SrTiO3)1-x-(SrTaO2N)x is tunable from 500 to 600 nm. The conduction band minimum (CBM) of (SrTiO3)1-x-(SrTaO2N)x comprises the Ti 3d orbitals and the Ta 5d orbitals, while the valence band maximum (VBM) consists of the O 2p and N 2p orbitals. The microstructure of the (SrTiO3)1-x‑(SrTaO2N)x consists of small nanoparticles, exhibiting a larger specific surface area than the parent compounds of SrTiO3 and SrTaO2N. In the photocatalytic hydrogen evolution reaction (HER) with sacrificial reagents, the activity of solid solutions is notably superior to that of nitrogen-doped SrTiO3 and SrTaO2N. This superiority is mainly attributed to its broad light absorption range and high charge separation efficiency, which indicates its potential as a promising photocatalytic material. Moreover, the magnesium powder-assisted nitridation method exhibits obvious advantages for the synthesis of oxynitrides and bears instructional significance for the synthesis of other nitrogen-containing compounds and even sulfur-containing compounds.

Quantitative analysis of organosulphur compounds in crude oil samples using magnetic solid phase extraction based on Au-Fe3O4 adsorbent and gas chromatography with time-of-flight mass spectrometry

AbstractThis study focused on the development of a magnetic solid phase extraction (m-SPE) method using Au-Fe3O4 as an adsorbent followed by GC-ToFMS analysis for the determination of organosulphur compounds (OSCs) in fuel samples. The m-SPE using Au-Fe3O4 NPs was preferred because of the low toxicity of the adsorbent1, high separation efficiency using external magnet2 and greater extraction selectivity between sulphur and Au atom3. The Au-Fe3O4 NPs were characterized using XRD, UV–Vis, TEM, SEM and FTIR. This method was optimized using multivariate analysis based on a two-level full factorial and central composite designs. The conditions which produced optimum efficiency were found to be 150 mg mass of sorbent, 100 µL eluent volume, 50 min extraction time and 6,5 pH of the sample. These optimum conditions showed a relatively low limit of detection in the range of 0.02–0.199nµg/g and limit of quantification of 0.08–0.602 µg/g. Furthermore, a relative standard deviation of triplicates analysis was between 0.8 and 2.3% with good linearity of 0.9816–0.9961. The percentage recovery for thiophene, 3-methylthiophene, benzothiophene and dibenzothiophene ranged from 76 to 95% for the spiked samples. The optimized m-SPE method was then applied in real fuel oil samples. The concentration of thiophene, 3-methylthiophene, benzothiophene and dibenzothiophene in crude oil, gasoline, diesel and kerosene ranged from 0.43–1.94 µg/g, 0.78–1.63 µg/g, 0.95–4.31 µg/g to 1.55–2.09 µg/g, respectively. The m-SPE, followed by GC-ToFMS method, proved to be efficient, inexpensive and an alternative method for OSCs analysis in fuel oils.

Unlocking Direct Lithium Extraction in Harsh Conditions through Thiol-Functionalized Metal-Organic Framework Subnanofluidic Membranes.

Metal-organic framework (MOF) membranes with high ion selectivity are highly desirable for direct lithium-ion (Li+) separation from industrial brines. However, very few MOF membranes can efficiently separate Li+ from brines of high Mg2+/Li+ concentration ratios and keep stable in ultrahigh Mg2+-concentrated brines. This work reports a type of MOF-channel membranes (MOFCMs) by growing UiO-66-(SH)2 into the nanochannels of polymer substrates to improve the efficiency of MOF membranes for challenging Li+ extraction. The resulting membranes demonstrate excellent monovalent metal ion selectivity over divalent metal ions, with Li+/Mg2+ selectivity up to 103 since Mg2+ should overcome a higher energy barrier than Li+ when transported through the MOF pores, as confirmed by molecular dynamics simulations. Under dual-ion diffusion, as the Mg2+/Li+ mole ratio of the feed solution increases from 0.2 to 30, the membrane Li+/Mg2+ selectivity decreases from 1516 to 19, corresponding to the purity of lithium products between 99.9 and 95.0%. Further research on multi-ion diffusion that involves Mg2+ and three monovalent metal ions (K+, Na+, and Li+, referred to as M+) in the feed solutions shows a significant improvement in Li+/Mg2+ separation efficiency. The Li+/Mg2+ selectivity can go up to 1114 when the Mg2+/M+ molar concentration ratio is 1:1, and it remains at 19 when the ratio is 30:1. The membrane selectivity is also stable for 30 days in a highly concentrated solution with a high Mg2+/Li+ concentration ratio. These results indicate the feasibility of the MOFCMs for direct lithium extraction from brines with Mg2+ concentrations up to 3.5 M. This study provides an alternative strategy for designing efficient MOF membranes in extracting valuable minerals in the future.

Tailoring the Structure-Property Relationship of Ring-Opened Metathesis Copolymers for CO2-Selective Membranes.

In this work, we explore the use of ring-opening metathesis polymerization (ROMP) facilitated by a second-generation Grubbs catalyst (G2) for the development of advanced polymer membranes aimed at CO2 separation. By employing a novel copolymer blend incorporating 4,4'-oxidianiline (ODA), 1,6-hexanediamine (HDA), 1-adamantylamine (AA), and 3,6,9-trioxaundecylamine (TA), along with a CO2-selective poly(ethylene glycol)/poly(propylene glycol) copolymer (Jeffamine2003) and polydimethylsiloxane (PDMS) units, we have synthesized membranes under ambient conditions with exceptional CO2 separation capabilities. The strategic inclusion of PDMS, up to a 20% composition within the PEG/PPG matrix, has resulted in copolymer membranes that not only surpass the 2008 upper limit for CO2/N2 separation but also meet the commercial targets for CO2/H2 separation. Comprehensive analysis reveals that these membranes adhere to the mixing rule and exhibit percolation behavior across the entire range of compositions (0-100%), maintaining robust antiplasticization performance even under pressures up to 20 atm. Our findings underscore the potential of ROMP in creating precisely engineered membranes for efficient CO2 separation, paving the way for their application in large-scale environmental and industrial processes.

The Influence of Ligands on the Pd-Catalyzed Diarylation of Vinyl Esters

The impact of ligands on the palladium-catalyzed 1,2-diarylation reaction course is presented. The application of Pd-dmpzc as a catalyst provides an efficient, chemoselective and sustainable protocol for the synthesis of valuable 1,2-diphenylethyl acetates. The reaction is conducted in water under mild conditions. Reaction products can be easily separated from the reaction mixture and catalyst by simple extraction. What is more, the rational choice of catalyst significantly reduces the leaching of the metal into the product and its contamination (0.1 ppm). Efficient phase separation and ultralow Pd leaching enable the reuse of the water medium containing the Pd-dmpzc catalyst several times without a significant loss of activity and with even higher selectivity (from 95% to 100% in the third cycle). The recyclability of both the catalyst and the reaction medium together with high chemoselectivity and low palladium leaching reduces the amount of waste and the cost of the process, exhibiting an example of a sustainable and green methodology.

Rapid and Comprehensive Analysis of 41 Harmful Substances in Multi-Matrix Products by Gas Chromatography–Mass Spectrometry Using Matrix-Matching Calibration Strategy

Harmful substances in consumer goods pose serious hazards to human health and the environment. However, due to the vast variety of consumer goods and the complexity of their substrates, it is difficult to simultaneously detect multiple harmful substances in different materials. This paper presents a method for the simultaneous determination of 41 harmful substances comprising 17 phthalates (PAEs), 8 organophosphate flame retardants (OPFRs), and 16 polycyclic aromatic hydrocarbons (PAHs) in five types of products using the matrix-matching calibration strategy. The method employs an efficient ultrasonic extraction procedure using a mixture of dichloromethane and methylbenzene, followed by dissolution–precipitation and analysis through gas chromatography–mass spectrometry. Compared with previous experiments, we established a universal pretreatment method suitable for multi-matrix materials to simultaneously determine multiple harmful substances. To evaluate the effects of the matrix on the experimental results, we compared neat standard solutions and matrix-matching standard solutions. The results demonstrated that all compounds were successfully separated within 30 min with excellent separation efficiency. Additionally, the linear relationships of all analytes showed strong correlation coefficients (R2) of at least 0.995, ranging from 0.02 mg/L to 20 mg/L. The average recoveries of the target compounds (spiked at three concentration levels) were between 73.6 and 124.1%, with a relative standard deviation (n = 6) varying from 1.2% to 9.9%. Finally, we tested 40 different materials from consumer products and detected 16 harmful substances in 31 samples. Overall, this method is simple and accurate, and it can be used to simultaneously determine multiple types of hazardous substances in multi-matrix materials by minimizing matrix effects, making it an invaluable tool for ensuring product safety and protecting public health.

Investigating Non-Newtonian Fluid Behavior in Hydrocyclones Via Computational Fluid Dynamics

Expert researchers examine complex patterns of pressure, viscosity, and velocity in a CFD study of viscoelastic food inside hydrocyclones to obtain a detailed grasp of particle behavior and fluid dynamics. Velocity profiles show how fluids and particles flow through the hydrocyclone in complex ways, while pressure distributions show where high and low pressure is found, regions that are critical for maximizing separation efficiency. Furthermore, the analysis of viscosity fluctuations clarifies the intricate relationship between fluid rheology and flow dynamics, providing information on how food's viscoelastic characteristics affect particle trajectories and separation efficiency. Utilizing this comprehensive examination, scientists hope to optimize the design and functioning parameters of the hydrocyclones, which will in turn improve the efficacy and efficiency of particle separation procedures in viscoelastic food solutions. This will ultimately lead to improvements in food processing technology and product quality. Researchers look into the impact of geometric elements on flow patterns and separation efficiency in addition to these characteristics, such as hydrocyclone size and inlet configurations. Additionally, they investigate how different operating parameters, such rotational speed and flow rate, affect how well the hydrocyclone handles viscoelastic food items. Through the integration of these complex analyses, researchers hope to create all encompassing models that can precisely forecast and optimize the behavior of viscoelastic food flows inside hydrocyclones, opening the door to improved process control and food sector product quality.

Intelligent Devices Harnessing Underwater Superoleophobic and Underoil Superhydrophobic Quartz Sands for the Separation of Diverse Stratified and Emulsified Water-Oil Mixtures.

To achieve the green, sustainable, and controllable recovery of oil-water resources and to address the limited functionality of single superwet materials in oil-water separation, this study reports a multifunctional oil-water separation strategy by compositing the underwater superoleophobic and underoil superhydrophobic materials (HS). The underwater superoleophobic quartz sands with an oil contact angle of 152.68° were prepared by adjusting the particle size. This material demonstrated a water flux of 4688 L m-2 h-1 and a low-density oil and water mixture separation efficiency of 98.6%, which remained above 97.9% over 50 cycles. It was effective in separating oil-in-water emulsions with a separation efficiency of >99%. For HS, quartz sands were modified with dodecyltrimethoxysilane. The optimized HS-4 exhibited superhydrophobic properties with a water contact angle of 157.06°. It achieved an oil flux of 5775 L m-2 h-1 and a water and dichloromethane mixture separation efficiency of 98.4%. Additionally, they exhibited significant potential in the separation of water-in-oil emulsions. Furthermore, by placing the underwater superoleophobic and underoil superhydrophobic units at the bottom of the filter, we achieved cyclic separation of high-density oil and water mixtures, low-density oil and water mixtures, water-in-oil emulsions, and oil-in-water emulsions. The separation efficiency consistently exceeded 96.5% over 10 cycles. In addition, the oil-water separation mechanism of underwater oleophobic and underoil hydrophobic materials was demonstrated by the relative concentration distribution of water and oil with molecular dynamics simulations. This intelligent oil-water separation method marks a significant advancement in the sustainable separation of diverse oil-water mixtures.

Perfect confinement of crown ethers in MOF membrane for complete dehydration and fast transport of monovalent ions.

Fast transport of monovalent ions is imperative in selective monovalent ion separation based on membranes. Here, we report the in situ growth of crown ether@UiO-66 membranes at a mild condition, where dibenzo-18-crown-6 (DB18C6) or dibenzo-15-crown-5 is perfectly confined in the UiO-66 cavity. Crown ether@UiO-66 membranes exhibit enhanced monovalent ion transport rates and mono-/divalent ion selectivity, due to the combination of size sieving and interaction screening effects toward the complete monovalent ion dehydration. Specifically, the DB18C6@UiO-66 membrane shows a permeation rate (e.g., K+) of 1.2 mol per square meter per hour and a mono-/divalent ion selectivity (e.g., K+/Mg2+) of 57. Theoretical calculations and simulations illustrate that, presumably, ions are completely dehydrated while transporting through the DB18C6@UiO-66 cavity with a lower energy barrier than that of the UiO-66 cavity. This work provides a strategy to develop efficient ion separation membranes via integrating size sieving and interaction screening and to illuminate the effect of ion dehydration on fast ion transport.

Regulating the Topology of Covalent Organic Frameworks for Boosting Overall H2O2 Photogeneration

AbstractPhotocatalytic oxygen reduction reactions and water oxidation reactions are extremely promising green approaches for massive H2O2 production. Nonetheless, constructing effective photocatalysts for H2O2 generation is critical and still challenging. Since the network topology has significant impacts on the electronic properties of two dimensional (2D) polymers, herein, for the first time, we regulated the H2O2 photosynthetic activity of 2D covalent organic frameworks (COFs) by topology. Through designing the linking sites of the monomers, we synthesized a pair of novel COFs with similar chemical components on the backbones but distinct topologies. Without sacrificial agents, TBD‐COF with cpt topology exhibited superior H2O2 photoproduction performance (6085 and 5448 μmol g−1 h−1 in O2 and air) than TBC‐COF with hcb topology through the O2‐O2⋅−‐H2O2, O2‐O2⋅−‐O21‐H2O2, and H2O‐H2O2 three paths. Further experimental and theoretical investigations confirmed that during the H2O2 photosynthetic process, the charge carrier separation efficiency, O2⋅− generation and conversion, and the energy barrier of the rate determination steps in the three channels, related to the formation of *OOH, *O21, and *OH, can be well tuned by the topology of COFs. The current study enlightens the fabrication of high‐performance photocatalysts for H2O2 production by topological structure modulation.